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Journal of Physics and Chemistry of Solids 72 (2011) 1170–1174

Contents lists available at ScienceDirect

Journal of Physics and Chemistry of Solids

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

A simple photochemical method to synthesize Ga2O3–Dy3 þ –M3 þ thin films

and their evaluation as optical materials (where M ¼ Cr or Co)
G. Cabello a,n, L. Lillo a, Y. Huentupil a, F. Cabrera a, G.E. Buono-Core b, B. Chornick c
a
Departamento de Ciencias Básicas, Facultad de Ciencias, Universidad del Bı́o-Bı́o, Chillán, Chile
b
Instituto de Quı́mica, Pontificia Universidad Católica de Valparaı́so, Valparaı́so, Chile
c
Departamento de Fı́sica, Facultad de Ciencias Fı́sicas y Matemáticas, Universidad de Chile, Casilla 487-3, Santiago 8370415, Chile

a r t i c l e i n f o a b s t r a c t

Article history: We report the photochemical method to synthesize Ga2O3–Dy3 þ –Co3 þ and Ga2O3–Dy3 þ –Cr3 þ thin
Received 6 May 2011 films. X-ray photoelectron spectroscopy, X-ray diffraction and photoluminescence were used to
Accepted 12 July 2011 characterize the products. These analyses revealed that as-deposited and annealed films are amor-
Available online 22 July 2011
phous. The optical characterization of the films showed that these are highly transparent in the visible
Keywords: spectrum but decrease significantly with doped and co-doped films. Under the excitation of UV light
A. Amorphous materials (254 nm) the doped films (Ga2O3–Dy3 þ ) show the characteristic emissions of Dy3 þ at 500, 575, 594,
D. Optical properties 605 and 652 nm corresponding to 4F9/2-6HJ ( J¼ 15/2, 13/2 and 11/2) transitions but the emissions
D. Luminescence decrease with the co-doped films (Ga2O3–Dy3 þ –M3 þ , where M ¼ Cr or Co); a possible emission
mechanism and energy transfer have been proposed.
& 2011 Elsevier Ltd. All rights reserved.

1. Introduction activators is of great importance in designing luminescent mate-

Gallium oxide (Ga2O3) is an important III–VI semiconductor,
which exhibits a wide band gap (Eg ¼4.9 eV) and it has potential
applications in optoelectronic devices including flat panel dis-
plays, solar energy conversion devices and ultraviolet emitters [1].
In general, Ga2O3 exhibits different polymorphic phases such as
rhombohedral a-, monoclinic b-, and cubic U- and s-phases and
all of them can be obtained from orthorhombic gallium oxide
hydroxide [a-GaO(OH)] simply by annealing at selective
temperature [1]. In recent years, several studies have reported
doping of this material with rare-earth (RE3 þ ) or 3d transition
metal ions; Ga2O3 thin films have also shown promising optical
and photo-luminescent (PL) properties [2]. It has been reported
[3] that b-Ga2O3 can exhibit UV, blue and green emissions,
depending on the sample preparation conditions and the nature
of defects, upon photo-excitation through the band gap. As to
photoluminescence of doped b-Ga2O3 their characteristic lumi-
nescence is produced due to d–d and f–f transitions of 3d
transition metal ions and RE3 þ ions, respectively [3]. The photo-
excitation mechanism through which doped ions emit visible
light has been ascribed to host-activator interactions or direct
intraconfigurational electronic transitions. Therefore, understand-
ing the relationship the trap state (defects) and luminescence of
rials based on gallium oxide.
Various growth techniques have been used to prepare thin
films of this material: spray pyrolysis deposition [4], sol–gel
process [5], radiofrequency (RF) magnetron sputtering [6] and
metal–organic chemical vapor deposition (MOCVD) [7].
In the present paper, we report the use of photo-chemical
method to prepare gallium oxide thin films co-doped with Dy3 þ
and Cr3 þ or Co3 þ . This method involves the UV irradiation of films
of suitable metal complexes precursors, which photo-decompose
on an appropriate substrate to leave on the surface thin films of
metals or metal oxides depending on the reaction conditions:
hv O2
MLn(thin film)! Mn  1 þnL(gas)! MOX(thin film) þsub-products
where M is the Ga, Dy, Cr or Co, L is the acac (2,4 pentandione)
and thd (2,2,6,6-tetramethyl-3,5-heptanedione).
In this paper we describe the use of the b-diketonate com-
plexes of gallium, dysprosium, chromium and cobalt to prepare
films of gallium oxide doped with Dy3 þ and co-doped with Cr3 þ
or Co3 þ and a preliminary study of their optical properties.
2. Experimental
2.1. General procedure

UV spectra were obtained with 1 nm resolution in a Perkin

n
Corresponding author. Tel.: þ56 42 253096; fax: þ 56 42 253046. Elmer Model Lambda 25 UV–vis spectrophotometer. X-ray dif-
E-mail address: gcabello@ubiobio.cl (G. Cabello). fraction patterns were obtained using a D8 Advance Bruker X-ray

0022-3697/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2011.07.013
 Author's personal copy
G. Cabello et al. / Journal of Physics and Chemistry of Solids 72 (2011) 1170–1174
diffractometer. The X-ray source was Cu 40 kV/40 mA. X-ray
photoelectron spectra (XPS) were recorded on an XPS-Auger
Perkin Elmer electron spectrometer Model PHI 1257, which
included an ultra high vacuum chamber, a hemispherical electron
energy analyzer and an X-ray source providing unfiltered Ka
radiation from its Al anode (hn ¼1486.6 eV). The pressure of the
main spectrometer chamber during data acquisition was main-
tained at ca.10  7 Pa. The binding energy (BE) scale was calibrated
using the peak of adventitious carbon, setting it to 284.6 eV. The
accuracy of the BE scale was 70.1 eV. Solid state photolysis was
carried out at room temperature under a low-pressure Hg lamp
(l ¼254 nm) equipped with two 6 W tubes, in air. Progress of the
reactions was monitored by determining the FT-IR spectra at
different time intervals, following the decrease in IR absorption of
the complexes. The substrates for deposition of films were
borosilicate glass microslides (Fischer, 2  2 cm2) and n-type
silicon (1 0 0) wafers (1  1 cm2) obtained from Wafer World
Inc., Florida, USA.
Photoluminescense (PL) emission spectra measurements were
carried out in an Ocean Optics Model QE65000-FL spectrometer
with an L type setup. Excitation was done with a PX-2 pulsed
Xenon lamp (220–750 nm), and the UV light passed through a
monochromator set to 254 nm. The measurements were done at
room temperature.
2.2. Preparation of amorphous thin films
The precursors Ga(III), Co(III), Cr(III) acetylacetonate com-
plexes and Dy tris(2,2,6,6-tetramethyl-3,5-heptanedionate)
complex were purchased from Aldrich Chemical Company and
thin films were prepared by the following procedure: a silicon
chip was placed on a spin coater and rotated at a speed of
1500 RPM. A portion (0.1 ml) of a solution of the precursor
complex in CH2Cl2 was dispensed onto the silicon chip and
allowed to spread. The motor was then stopped after 30 s and a
thin film of the complex remained on the chip. The quality of the
films by optical microscopy was examined (500  magnification).
2.3. Photolysis of complexes as films on Si (1 0 0) surfaces
All photolysis experiments were conducted following the same
procedure: a film of the complex was deposited on n-type Si
(1 0 0) by spin-coating from a CH2Cl2 solution. This resulted in
the formation of a smooth, uniform coating on the chip. The
quality (uniformity, defects, etc.) of the precursor films was
determined by optical microscopy (500  ), while the thickness
2.0
1.8 t0
1.6
1.4
Absorbance
1.2
1.0
0.8
0.6
0.4
0.2
0.0
250 275 300 325 350
Wavelength (nm)
Fig. 1. Changes in the UV spectrum of a solution in CH2Cl2 of (a) Ga(acac)3 complex (4.09  10  5 mol/L) upon 307 min irradiation and (b) Dy(thd)3 complex
(1.32  10  4 mol/L) upon 398 min irradiation with 254 nm light.
1171
was monitored by interferometry. The FT-IR spectrum of the
starting film was first obtained. The irradiation of the films was
carried out at room temperature using two low-pressure Hg
lamps (6 W, Rayonet RPR—2537 A) in air, until the FT-IR spec-
trum showed no evidence of the starting material. Prior to
analysis, the chip was rinsed several times with dry acetone to
remove any organic products remaining on the surface. In order
to obtain films of a specific thickness, successive layers of the
precursors were deposited by spin-coating and irradiated as
above. This process was repeated several times until the desired
thickness was achieved. Post-annealing was carried out under a
continuous flow of synthetic air at 800 1C for 3 h in a program-
mable Lindberg tube furnace.
3. Results and discussion
3.1. Photochemistry of Ga(III) and Dy(III) b-diketonate complexes
The photochemistry of metal b-diketonate complexes has been
widely investigated [8–10], because they absorb strongly at
readily accessible parts of the UV spectrum (250–400 nm). In
general, the irradiation of these complexes with UV light
(254 nm) leads to the photo-reduction of these complexes, upon
LMCT (ligand-to-metal charge transfer) excitation to form metals.
In this case no reports can be found in the literature concerning
Ga(acac)3 and Dy(thd)3 complexes. We therefore carried out
experiments to evaluate the photo-reactivity of these complexes
in solution as a film. When dichloromethane solutions of these
complexes were photolyzed with 254 nm UV light, a complete
disappearance of the absorption bands of these complexes could
be observed after 300 min of irradiation (Fig. 1). The electronic
spectra of Ga(III) and Dy(III) b-diketonate complexes exhibited
bands at 285 and 275 nm, respectively. The observed absorption
bands have been assigned to the various electronic transitions. In
dichloromethane diluted solutions, irradiation of the Ga(acac)3
complex at 254 nm provoked fast spectral changes consisting of
decreases of the absorption band at 285 nm and slight shift of the
band at 274 nm, which is characteristic of the free 2,4-pentan-
dione ligand (Hacac) associated with a p–p* (HOMO-LUMO)
transition [11,12], which also degrades (Fig. 1a).
On the other hand, the Dy(thd)3 complex exhibits a single
band at 275 nm, attributable to ligand transition of a p–p*, the
break of hydrogen intraligand bond, present in the enol form of
the ligand, and the formation of two hydrogen intermolecular
bonds with the solvent, giving an electronic situation similar to
2.0
1.8
1.6 t0
1.4
Absorbance
1.2
1.0
0.8
0.6
0.4
0.2
0.0
375 400 250 275 300 325 350 375 400
Wavelength (nm)
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1172 G. Cabello et al. / Journal of Physics and Chemistry of Solids 72 (2011) 1170–1174

the complex. The irradiation of the Dy(thd)3 complex in dichlor- centers at 531.1 eV, generally, the O 1s peak has been observed at the
omethane diluted solutions at 254 nm provoked complete degra- binding energy of 528–535 eV [13]. The peak around 530.5–531.8 eV
dation of the complex, as evidenced by a gradual disappearance of is usually attributed to oxygen in non-stoichiometric oxides, while
the band at 275 nm (Fig. 1b). These results demonstrate that the peak of chemisorbed O2 is located in the region of 532–535 eV
these complexes are highly photo-reactive in solution; the excita- [15]. The binding energy of Dy 4d is situated at 154.1 eV, associated
tion at 254 nm light generates a series of intermediaries or with a Dy(III) species; similar values have been reported by other
sub-products that facilitate the photo-reduction of metal species authors [16,17]. According to the literature data, the Cr 2p3/2 peak of
present in the complexes. pure Cr2O3 is at a BE of 576 eV, whereas that of pure chromium
In order to investigate the solid-state photochemistry, films of metal is at a BE of 574 eV [18,19]. In this case the Cr 2p3/2 is located
the Ga(acac)3 and Dy(thd)3 complexes were irradiated under air at 576.8 eV. On the other hand it has been established that for the Co
atmosphere with a 254 nm UV lamps. This led to a decrease of the 2p signal the Co 2p3/2 and Co 2p1/2 spin–orbit components are
absorptions associated with the ligand, as shown in the FT-IR located at 780 and 796 eV, respectively [20]. For the Co 2p3/2 peak
monitoring of the reaction (not shown here). These results has been identified in several phases at 779.5, 780.7, 781.6 and
suggest that the complex precursors are photo-dissociated 777.5 eV corresponding to Co3O4, CoO, Co2O3 and metallic Co [21].
on the surface forming volatile products, which are partially Our studies indicate that the Co 2p3/2 peak is situated at 780.1 eV
desorbed. Exhaustive photolysis results in the loss of the all associated with the Co3O4 formation.
bands associated with the starting complexes. In order to investigate the effect of thermal annealing at 800 1C
for 3 h on the Ga2O3–Dy3 þ –M3 þ thin films, we have performed an
3.2. Characterization of Ga2O3–Dy3 þ –M3 þ thin films XRD analysis on the co-doped films, the XRD patterns were
(where M¼Cr or Co) featureless, except for the reflection from Si(1 0 0) located at
2y ¼33.11, thereby indicating the amorphous nature of the films
For the photo-deposition of Ga2O3 co-doped with Dy3 þ and (Fig. 3). Similar results were obtained using Ga(acac)3 as precursors
transition metal ions thin films, solutions of Ga(acac)3 with for the deposition of Ga2O3 thin films by MOCVD at 700 1C [22].
10 mol% proportions of the Dy(thd)3 and M(acac)3 were spin
coated on the appropriate substrate and the thin films co-doped 3.2.2. Optical measurements
were irradiated for 24 h until minimal absorptions in the infrared The thickness of the films used for optical measurement was
spectrum from the complexes were observed. about 400 nm. Fig. 4 shows the transmittance (%) spectrum for
Ga2O3, Ga2O3–Dy3 þ and Ga2O3–Dy3 þ –M3 þ thin films. In general
3.2.1. XPS and XRD analysis the undoped Ga2O3 shows a transmittance of about 90% in the
The elemental composition of the as-deposited Ga2O3 co- wavelength range from 400 to 900 nm, and this is slightly
doped thin films was analyzed by XPS, in order to study the reduced as it enters in the UV region. However, the transmittance
chemical nature of the deposited surface. Fig. 2 shows the wide of the doped and co-doped thin films decreases significantly.
scan XPS spectrum, in the binding energy (BE) range 0–1200 eV. A high optical transmission in the visible region is required for
The spectrum shows signals from Ga 2p, Ga LMM (Auger peaks) luminescent materials to obtain the effective emission.
O 1s, Dy 4d, Cr 2p, Co 2p3 and C 1s. The carbon detected on the On the other hand, the high transparency of the annealed thin
as-deposited films is probably the result of an organic residue films indicates fairly smooth surfaces and low thickness due to
from organic raw precursors. relative film homogeneity.
The peaks of Ga 2p1/2 and Ga 2p3/2 are located at the binding To determine the optical band gap of these films, from the (ahv)2
energy of 1144.8 and 1118.0 eV, respectively, and that corresponding vs. hv has been plotted and extrapolated and the linear portion of
to Ga–O bonding, which are consistent with other experimental the curve has been extrapolated to a ¼0 (inset of Fig. 4), in which a
results [6,13,14]. The core level of gallium has a positive shift from and hv are the absorption coefficient and photon energy, respec-
elemental gallium [13], which indicates that the gallium present in tively. The absorption coefficient increases rapidly at the photon
the films is in compound state, not in elemental state. The O 1s peak energy range around 4.0–5.0 eV. The result indicates that the

250 45
Ga 2p3
Ga 2p1

40 Si (100)
200
Co 2p3

Co LMM

O 1s

35
O KLL

Ga LMM 1
Ga LMM
Intensity (a.u.)

30
Dy 4p3

Intensity (a. u.)

150
Dy 4d
Ga 3p
Cr LMM 1

25
Cr 2p3
Cr 2p1

Dy 4p3

100 20
Dy 4d

15
50 10

5
0
1200 1000 800 600 400 200 0 0
Binding Energy (eV) 30 35 40 45 50 55 60 65 70
2 theta (degree)
Fig. 2. XPS survey scan of an as-deposited of (a) Ga2O3 (b) Ga2O3–Dy3 þ –Cr3 þ and
(c) Ga2O3–Dy3 þ –Co3 þ thin films obtained by UV irradiation at 254 nm on Si(1 0 0) Fig. 3. XRD patterns of (a) Ga2O3–Dy3 þ –Cr3 þ and (b) Ga2O3–Dy3 þ –Co3 þ thin
substrates. films annealed at 800 1C for 3 h on Si (1 0 0) substrates.
 Author's personal copy
G. Cabello et al. / Journal of Physics and Chemistry of Solids 72 (2011) 1170–1174
100
90
(1)
80
Trasmittance (%)
(2)
70
(3)
60
(4)
50
40 (1) Ga O
(2) Ga O -Dy
30
(3) Ga O -Dy -Cr
20 (4) Ga O -Dy -Co
10
200 300 400 500 600 700
Wavelength (nm)
Fig. 4. Transmission spectra for the Ga2O3–Dy3 þ –M3 þ thin films. (Inset) Square of absorption coefficient as a function of photon energy for Ga2O3–Dy3 þ –M3 þ
(a) as-deposited and (b) annealed thin films.
Table 1
Measured optical band gap (eV).
Sample Ga2O3 Ga2O3–Dy3 þ Ga2O3–Dy3 þ –Cr3 þ Ga2O3–Dy3 þ –Co3 þ
As-deposited 4.8 7 0.1 4.7 70.1 4.5 7 0.1
Annealed 4.9 7 0.1 4.7 70.1 4.6 7 0.1
absorption in this energy region is due to the direct transition. The
band gap was estimated to be 4.870.1 eV for undoped Ga2O3 films,
which agrees with the values reported [5,23]. Our measured optical
band gap values of Ga2O3–Dy3 þ and Ga2O3–Dy3 þ –M3 þ thin films
for the as-deposited and annealed films are shown in Table 1. In
general the band gap values decrease slightly with the doping and
co-doping of the Ga2O3 films. These values are too large to absorb
and utilize visible light. It has been reported that incorporation of
metal ions into the Ga2O3 thin films resulted in shifts in the
absorption spectra. This observation suggests that impurity levels
are introduced between the intrinsic bands, which subsequently
generate new band gaps [24]. The effects that dopants have on the
performance of Ga2O3 are mainly associated with modifying the
microstructure as well as reducing the band gaps. However, our
results are not showing significant changes in the values of the
band gaps because, our films still have an amorphous structure
after subjecting them to heat treatment.
3.2.3. Photoluminescence study
Fig. 5 shows the photoluminescence (PL) spectra of Ga2O3
doped and co-doped samples under excitation at 254 nm. It is
known that the luminescence of trivalent dysprosium Dy3 þ
mainly consists of narrow lines in the blue region (470–500 nm)
and yellow region (570–600 nm). The two emissions have origi-
nated from 4F9/2-6H15/2 and 4F9/2-6H13/2 transitions of Dy3 þ
[25]. The 4F9/2-6H13/2 transition is hypersensitive and its inten-
sity strongly depends on the host, in contrast to a less sensitive
4
F9/2-6H15/2 transition of Dy3 þ [26].
Our experimental results in Fig. 5 show PL from 450–700 nm
of all samples. No signals associated to undoped Ga2O3 thin films.
However for the films doped with Dy3 þ (Ga2O3–Dy3 þ ) show a
series of peaks located at 500, 575, 594, 605, 622 and 652 nm. The
signal at 500 nm is assigned to the transition of Dy3 þ ion from the
4
F9/2 excited state to the 6H15/2 ground state. The signals at 575,
594 and 605 nm correspond to 4F9/2-6H13/2 transition and the
peak situated at 652 nm is attributed to the 4F9/2-6H11/2 transi-
tion of Dy3 þ ion. On the other hand, for the co-doped films
1173
100
(1)
90
(2)
80
Transmittance (%)
(3) (4)
70 (4) (3)
60
50
(1) Ga O (2)
40
(2) Ga O -Dy (1)
30 (3) Ga O -Dy -Cr
20 (4) Ga O -Dy -Co
800 900 200 300 400 500 600 700 800 900
Wavelength (nm)
(Ga2O3–Dy3 þ –Cr3 þ and Ga2O3–Dy3 þ –Co3 þ ), it is possible to
observe the same spectral pattern of the signals but their
intensities decreased significantly. There are no signals that can
be assigned to Cr3 þ or Co3 þ ions.
4.5 70.1 It should be noted that both as-deposited and annealed
4.5 70.1 samples showed the same pattern of spectral behavior (see
Fig. 5a and b). It has been reported [27] that local structural
environments and spatial distribution of dopants when develop-
ing a nano-sized luminescent material activated by RE elements
because absorption and emission properties of intra-4f-config-
urational transitions of RE ions are sensitive to their chemical and
structural status in a host. In this case given the amorphous
nature of all as-deposited and annealed films, there was no
significant structural change to produce a noticeable change in
the PL emissions.
However the PL of samples annealed at 800 1C (Fig. 5b) shows
that their emission intensity slightly decreases in comparison
with the signals from the as-deposited samples (Fig. 5b), we have
obtained similar results in other works [28,29] where the anneal-
ing samples at high temperature decrease the excitation effi-
ciency and the corresponding emission due to the loss of oxygen
weakly absorbed on the surface of the films that can act as a
bridge to enhance the bonding state of activator (Dy3 þ ions) with
O–Ga of the material host and thus improve the energy transfer
process. When the samples are further annealed at 800 1C, the
host defect of band gap excitation suddenly disappears and the
luminescence quenches.
However, it is observed that co-doping of transition metals
remarkably influences PL properties of the Ga2O3–Dy3 þ films; in
this case the concentration of 10 mol% of co-dopant decreases the
PL properties of the Ga2O3–Dy3 þ films; the presence of Co3 þ or
Cr3 þ ions at 10 mol% may act as PL killers due to the energy
transfer from excited Dy3 þ to Co3 þ or Cr3 þ ions. On the other
hand, co-doping at this level of concentration leads to an increase
of surface defects that will be involved and the non-radiative
relaxation rate will increase. PL studies of TiO2:Sm3 þ prepared by
the sol–gel method have shown that on co-doping with different
amounts of Br  [30] or Bi3 þ or Zr4 þ [31] the PL intensities
decrease when the co-dopant concentration is 41 mol%.
Based on the results obtained by other authors [30–32], similar
to those obtained in this work, we proposed a model of energy
transfer to explain why the co-doping in the films causes a
reduction in the PL emissions of Dy3 þ ion. This co-doping system
is proposed in Fig. 6. (1) under 254 nm irradiation (band
gap excitation) the generation process of excitations from the
valence band (VB) to the conduction band (CB) is produced;
 Author's personal copy

1174 G. Cabello et al. / Journal of Physics and Chemistry of Solids 72 (2011) 1170–1174

80000 60000

575 nm

575 nm
70000 50000

500 nm

500 nm
60000

622 nm
Intensity (a. u.)
622 nm
40000
Intensity (a.u.)

(4)
50000

594 nm
605 nm

594 nm
(4)

605 nm
40000 30000
(3)

652 nm

652 nm
30000 (3)
(2) 20000
20000 (1) (2)
(1)
10000
10000

0 0
450 500 550 600 650 700 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

Fig. 5. PL spectra of (a) as-deposited and (b) annealed films at 800 1C of the samples: (1) Ga2O3; (2) Ga2O3–Dy3 þ –Co3 þ ; (3) Ga2O3–Dy3 þ –Cr3 þ and (4) Ga2O3–Dy3 þ
thin films.

Acknowledgments

The authors are grateful to the financial support of the

FONDECYT (National Fund for Scientific and Technological Devel-
opment), Chile, Grant no. 1100045 and Direccion de Investigacion
de la U. del Bıo-Bıo, DIUBB proyect. Grant no. 092509 3/R.

References

[1] G. Sinha, A. Patra, Chem. Phys. Lett. 473 (2009) 151.

[2] P. Marie, X. Portier, J. Cardin, Phys. Status Solidi A 205 (2008) 1943.
[3] S. Fujihara, Y. Shibata, J. Lumin. 121 (2006) 470.
[4] Z. Ji, J. Du, J. Fan, W. Wang, Opt. Mater. 28 (2006) 415.
[5] G. Sinha, K. Adhikary, S. Chaudhuri, Opt. Mater. 29 (2007) 718.
[6] Q. Xu, S. Zhang, Superlattices Microstruct. 44 (2008) 715.
[7] H. Woo Kim, N. Ho Kim, J. Alloys Compd. 389 (2005) 177.
[8] B. Marciniak, G.E. Buono-Core, J. Photochem. Photobiol. A: Chem. 52 (1990) 1.
[9] S. Giuffrida, G. Condorelli, L. Costanzo, I. Fragala, G. Ventimiglia, G. Vecchio,
Chem. Mater. 16 (2004) 1260.
[10] S. Giuffrida, G. Condorelli, L. Costanzo, G. Ventimiglia, R. Lo Nigro, M. Favazza,
E. Votrico, C. Bongiorno, I. Fragala, J. Nanoparticle. Res. 9 (2007) 611.
Fig. 6. A simple model illustrating the emission process in Ga2O3–Dy3 þ thin films [11] S. Giuffrida, L. Costanzo, G. Condorelli, G. Ventimiglia, I. Fragala, Inorg. Chim.
and the energy transfer from Ga2O3–Dy3 þ –M3 þ thin films (M¼ Cr or Co). Acta 358 (2005) 1873.
[12] C. Crisafulli, S. Scire, S. Giuffrida, G. Ventimiglia, R. Lo Nigro, Appl. Catal.
A: Gen. 306 (2006) 51.
(2) the electrons move freely in the CB and finally relaxes to the
[13] L. Qin, C. Xue, Y. Duan, L. Shi, Physica B 404 (2009) 190.
donor band (oxygen vacancies) or directly to 4F9/2 excited state [14] F. Shi, S. Zhang, C. Xue, J. Alloys Compd. 498 (2010) 77.
level of Dy3 þ ; (3) the emission process occurs due to the [15] J.C. Dupin, D. Gonbeau, P. Vinater, A. Levasseur, Phys. Chem. Chem. Phys. 2
transitions from the excited state 4F9/2 to the ground levels of (2000) 1319.
6 [16] M. Salavati-Niasari, J. Javidi, F. Davar, A. Amini Fazl, J. Alloys Compd. 503
H15/2, 6H13/2 and 6H11/2 from Dy3 þ . These emission processes are (2010) 500.
reduced by (4) the presence of defects caused by co-doping of [17] A.K. Bakshi, S.N. Jha, L. Olivi, D.M. Phase, R.K. Kher, D. Bhattacharyya, Nucl.
Cr3 þ or Co3 þ that produces the non-radiative energy transfer Instrum. Methods Phys. Res. B 264 (2007) 109.
[18] %
S. Surviliene_ , V. Jasulaitiene_ , A. Češunien e_ , A. Lisowska-Oleksiak, Solid State
from the excited state of Dy3 þ to defects of the transition metals, Ionics 179 (2008) 222.
leading to the decrease of emission intensity (5) and process of [19] M.F. Al-Kuhaili, S.M.A. Durrani, Opt. Mater. 29 (2007) 709.
non-radiative transitions of transition metal (M). [20] A. Gulino, I. Fragala, Inorg. Chim. Acta 358 (2005) 4466.
[21] A. Avila, G.E. Barrera, C.L. Huerta, A.S. Muhl, Sol. Energy Mater. Sol. Cells 82
(2004) 269.
[22] M. Hellwig, Ke Xu, D. Barreca, A. Gasparotto, M. Winter, E. Tondello,
R. Fischer, A. Devi, Eur. J. Inorg. Chem. (2009) 1110.
4. Conclusions [23] G. Sinha, K. Adhikary, S. Chaudhuri, J. Cryst. Growth 276 (2005) 204.
[24] S. Chang, R. Doong, J. Phys. Chem. B 108 (2004) 18098.
The Ga2O3–Dy3 þ –Co3 þ and Ga2O3–Dy3 þ –Cr3 þ thin films, were [25] L.A. Diaz-Torres, E. De la Rosa, P. Salas, V.H. Romero, C. Angeles-Chávez,
J. Solid State Chem. 181 (2008) 75.
successfully prepared by a simple photochemical method. The [26] J. Pisarska, Opt. Mater. 31 (2009) 1784.
compositional and structural characterization of the samples using [27] S.K. Pillai, L.M. Sikhwivhilu, T.K. Hillie, Mater. Chem. Phys. 120 (2010) 619.
XPS and XRD, respectively, revealed the Ga2O3 formation for the [28] G. Cabello, L. Lillo, C. Caro, B. Chornik, M.A. Soto, R. del Rı́o, M. Tejos, J. Phys.
Chem. Solids. 71 (2010) 1367.
host material and Dy(III), Cr(III) or Co(III) as activators and the
[29] G. Cabello, L. Lillo, C. Caro, G.E. Buono-Core, B. Chornik, M.A. Soto, J. Non-
amorphous structure of the films. The emission spectra of the Dy3 þ Cryst. Solids 354 (2008) 3919.
doped samples showed characteristic 4F9/2-6HJ (J ¼ 15/2, 13/2 and 11/2) [30] C. Gao, H. Song, L. Hu, G. Pan, R. Qin, F. Wang, Q. Dai, L. Fan, L. Liu, H. Liu,
transitions, but these emissions decreased with the co-doped films. J. Lumin. 128 (2008) 559.
[31] L. Hu, H. Song, G. Pan, B. Yan, R. Qin, Q. Dai, L. Fan, S. Li, X. Bai, J. Lumin. 127
A study of decay times or decay processes of PL is necessary to verify (2007) 371.
the proposed mechanism in the present preliminary study. [32] K.L. Frindell, M.H. Bartl, J. Solid State Chem. 172 (2003) 81.