This article appeared in a journal published by Elsevier.

The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elseviers archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright

Author's personal copy

Journal of Physics and Chemistry of Solids 72 (2011) 11701174

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 Ga2O3Dy3 M3 thin lms and their evaluation as optical materials (where M 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 Basicas, Facultad de Ciencias, Universidad del Bo-Bo, Chillan, Chile so, Valpara so, Chile Instituto de Qumica, Ponticia Universidad Catolica de Valpara c Departamento de Fsica, Facultad de Ciencias Fsicas y Matematicas, Universidad de Chile, Casilla 487-3, Santiago 8370415, Chile
b

a r t i c l e i n f o
Article history: Received 6 May 2011 Accepted 12 July 2011 Available online 22 July 2011 Keywords: A. Amorphous materials D. Optical properties D. Luminescence

a b s t r a c t
We report the photochemical method to synthesize Ga2O3Dy3 Co3 and Ga2O3Dy3 Cr3 thin lms. X-ray photoelectron spectroscopy, X-ray diffraction and photoluminescence were used to characterize the products. These analyses revealed that as-deposited and annealed lms are amorphous. The optical characterization of the lms showed that these are highly transparent in the visible spectrum but decrease signicantly with doped and co-doped lms. Under the excitation of UV light (254 nm) the doped lms (Ga2O3Dy3 ) show the characteristic emissions of Dy3 at 500, 575, 594, 605 and 652 nm corresponding to 4F9/2-6HJ ( J 15/2, 13/2 and 11/2) transitions but the emissions decrease with the co-doped lms (Ga2O3Dy3 M3 , where M Cr or Co); a possible emission mechanism and energy transfer have been proposed. & 2011 Elsevier Ltd. All rights reserved.

1. Introduction Gallium oxide (Ga2O3) is an important IIIVI semiconductor, which exhibits a wide band gap (Eg 4.9 eV) and it has potential applications in optoelectronic devices including at panel displays, 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 ) or 3d transition metal ions; Ga2O3 thin lms 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 luminescence is produced due to dd and ff transitions of 3d transition metal ions and RE3 ions, respectively [3]. The photoexcitation mechanism through which doped ions emit visible light has been ascribed to host-activator interactions or direct intracongurational electronic transitions. Therefore, understanding the relationship the trap state (defects) and luminescence of

activators is of great importance in designing luminescent materials based on gallium oxide. Various growth techniques have been used to prepare thin lms of this material: spray pyrolysis deposition [4], solgel process [5], radiofrequency (RF) magnetron sputtering [6] and metalorganic chemical vapor deposition (MOCVD) [7]. In the present paper, we report the use of photo-chemical method to prepare gallium oxide thin lms co-doped with Dy3 and Cr3 or Co3 . This method involves the UV irradiation of lms of suitable metal complexes precursors, which photo-decompose on an appropriate substrate to leave on the surface thin lms of metals or metal oxides depending on the reaction conditions: MLn(thin
lm)!

hv

Mn 1 nL(gas)! MOX(thin

O2

lm) sub-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 complexes of gallium, dysprosium, chromium and cobalt to prepare lms of gallium oxide doped with Dy3 and co-doped with Cr3 or Co3 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 Elmer Model Lambda 25 UVvis spectrophotometer. X-ray diffraction patterns were obtained using a D8 Advance Bruker X-ray

Corresponding author. Tel.: 56 42 253096; fax: 56 42 253046. E-mail address: gcabello@ubiobio.cl (G. Cabello).

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) 11701174 1171

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 unltered Ka radiation from its Al anode (hn 1486.6 eV). The pressure of the main spectrometer chamber during data acquisition was maintained 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 254 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 lms 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 (220750 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 lms The precursors Ga(III), Co(III), Cr(III) acetylacetonate complexes and Dy tris(2,2,6,6-tetramethyl-3,5-heptanedionate) complex were purchased from Aldrich Chemical Company and thin lms 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 lm of the complex remained on the chip. The quality of the lms by optical microscopy was examined (500 magnication). 2.3. Photolysis of complexes as lms on Si (1 0 0) surfaces All photolysis experiments were conducted following the same procedure: a lm 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 lms was determined by optical microscopy (500 ), while the thickness

was monitored by interferometry. The FT-IR spectrum of the starting lm was rst obtained. The irradiation of the lms was carried out at room temperature using two low-pressure Hg lamps (6 W, Rayonet RPR2537 A) in air, until the FT-IR spectrum 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 lms of a specic 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 ow of synthetic air at 800 1C for 3 h in a programmable 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 [810], because they absorb strongly at readily accessible parts of the UV spectrum (250400 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 lm. 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-pentandione ligand (Hacac) associated with a pp* (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 pp*, 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 1.4

Absorbance Absorbance

2.0 t0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250 275 300 325 350 Wavelength (nm) 375 400 250 275 300 325 350 Wavelength (nm) 375 400 t0

1.2 1.0 0.8 0.6 0.4 0.2 0.0

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.

Author's personal copy

1172 G. Cabello et al. / Journal of Physics and Chemistry of Solids 72 (2011) 11701174

the complex. The irradiation of the Dy(thd)3 complex in dichloromethane diluted solutions at 254 nm provoked complete degradation of the complex, as evidenced by a gradual disappearance of the band at 275 nm (Fig. 1b). These results demonstrate that these complexes are highly photo-reactive in solution; the excitation at 254 nm light generates a series of intermediaries or sub-products that facilitate the photo-reduction of metal species present in the complexes. In order to investigate the solid-state photochemistry, lms of the Ga(acac)3 and Dy(thd)3 complexes were irradiated under air atmosphere with a 254 nm UV lamps. This led to a decrease of the absorptions associated with the ligand, as shown in the FT-IR monitoring of the reaction (not shown here). These results suggest that the complex precursors are photo-dissociated on the surface forming volatile products, which are partially desorbed. Exhaustive photolysis results in the loss of the all bands associated with the starting complexes. 3.2. Characterization of Ga2O3Dy3 M3 thin lms (where MCr or Co) For the photo-deposition of Ga2O3 co-doped with Dy3 and transition metal ions thin lms, solutions of Ga(acac)3 with 10 mol% proportions of the Dy(thd)3 and M(acac)3 were spin coated on the appropriate substrate and the thin lms co-doped were irradiated for 24 h until minimal absorptions in the infrared spectrum from the complexes were observed. 3.2.1. XPS and XRD analysis The elemental composition of the as-deposited Ga2O3 codoped thin lms was analyzed by XPS, in order to study the chemical nature of the deposited surface. Fig. 2 shows the wide scan XPS spectrum, in the binding energy (BE) range 01200 eV. The spectrum shows signals from Ga 2p, Ga LMM (Auger peaks) O 1s, Dy 4d, Cr 2p, Co 2p3 and C 1s. The carbon detected on the as-deposited lms is probably the result of an organic residue from organic raw precursors. The peaks of Ga 2p1/2 and Ga 2p3/2 are located at the binding energy of 1144.8 and 1118.0 eV, respectively, and that corresponding to GaO bonding, which are consistent with other experimental results [6,13,14]. The core level of gallium has a positive shift from elemental gallium [13], which indicates that the gallium present in the lms is in compound state, not in elemental state. The O 1s peak

centers at 531.1 eV, generally, the O 1s peak has been observed at the binding energy of 528535 eV [13]. The peak around 530.5531.8 eV is usually attributed to oxygen in non-stoichiometric oxides, while the peak of chemisorbed O2 is located in the region of 532535 eV [15]. The binding energy of Dy 4d is situated at 154.1 eV, associated with a Dy(III) species; similar values have been reported by other authors [16,17]. According to the literature data, the Cr 2p3/2 peak of pure Cr2O3 is at a BE of 576 eV, whereas that of pure chromium metal is at a BE of 574 eV [18,19]. In this case the Cr 2p3/2 is located at 576.8 eV. On the other hand it has been established that for the Co 2p signal the Co 2p3/2 and Co 2p1/2 spinorbit components are located at 780 and 796 eV, respectively [20]. For the Co 2p3/2 peak has been identied in several phases at 779.5, 780.7, 781.6 and 777.5 eV corresponding to Co3O4, CoO, Co2O3 and metallic Co [21]. Our studies indicate that the Co 2p3/2 peak is situated at 780.1 eV associated with the Co3O4 formation. In order to investigate the effect of thermal annealing at 800 1C for 3 h on the Ga2O3Dy3 M3 thin lms, we have performed an XRD analysis on the co-doped lms, the XRD patterns were featureless, except for the reection from Si(1 0 0) located at 2y 33.11, thereby indicating the amorphous nature of the lms (Fig. 3). Similar results were obtained using Ga(acac)3 as precursors for the deposition of Ga2O3 thin lms by MOCVD at 700 1C [22]. 3.2.2. Optical measurements The thickness of the lms used for optical measurement was about 400 nm. Fig. 4 shows the transmittance (%) spectrum for Ga2O3, Ga2O3Dy3 and Ga2O3Dy3 M3 thin lms. In general the undoped Ga2O3 shows a transmittance of about 90% in the wavelength range from 400 to 900 nm, and this is slightly reduced as it enters in the UV region. However, the transmittance of the doped and co-doped thin lms decreases signicantly. A high optical transmission in the visible region is required for luminescent materials to obtain the effective emission. On the other hand, the high transparency of the annealed thin lms indicates fairly smooth surfaces and low thickness due to relative lm homogeneity. To determine the optical band gap of these lms, from the (ahv)2 vs. hv has been plotted and extrapolated and the linear portion of the curve has been extrapolated to a 0 (inset of Fig. 4), in which a and hv are the absorption coefcient and photon energy, respectively. The absorption coefcient increases rapidly at the photon energy range around 4.05.0 eV. The result indicates that the

250
Ga 2p1 Ga 2p3

45 40
Co 2p3 Co LMM O 1s O KLL Ga LMM Ga LMM 1

Si (100)

200
Intensity (a.u.)

35
Dy 4p3

Dy 4d

Cr LMM 1

Ga 3p

150

Intensity (a. u.)

30 25 20 15 10 5

Cr 2p1 Cr 2p3

50

0 1200

Dy 4d

100

Dy 4p3

1000

800 600 400 Binding Energy (eV)

200

0 30 35 40 45 50 55 2 theta (degree) 60 65 70

Fig. 2. XPS survey scan of an as-deposited of (a) Ga2O3 (b) Ga2O3Dy3 Cr3 and (c) Ga2O3Dy3 Co3 thin lms obtained by UV irradiation at 254 nm on Si(1 0 0) substrates.

Fig. 3. XRD patterns of (a) Ga2O3Dy3 Cr3 and (b) Ga2O3Dy3 Co3 thin lms 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) 11701174 1173

100 90 80
Trasmittance (%)
(1)

100
(1)

90

Transmittance (%)

80 70 60 50 40 30 20

(2) (3) (4)

(4) (3)

70 60 50 40 30 20 10 200

(2) (3) (4) (1) Ga O (2) Ga O -Dy (3) Ga O -Dy -Cr (4) Ga O -Dy -Co

(1) Ga O (2) Ga O -Dy (3) Ga O -Dy -Cr (4) Ga O -Dy -Co

(2) (1)

300

400 500 600 700 Wavelength (nm)

800

900

200

300

400 500 600 700 Wavelength (nm)

800

900

Fig. 4. Transmission spectra for the Ga2O3Dy3 M3 thin lms. (Inset) Square of absorption coefcient as a function of photon energy for Ga2O3Dy3 M3 (a) as-deposited and (b) annealed thin lms.

Table 1 Measured optical band gap (eV).

Sample Ga2O3 Ga2O3Dy3 Ga2O3Dy3 Cr3 Ga2O3Dy3 Co3 4.5 7 0.1 4.6 7 0.1 4.5 70.1 4.5 70.1

As-deposited 4.8 7 0.1 4.7 70.1 Annealed 4.9 7 0.1 4.7 70.1

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 lms, which agrees with the values reported [5,23]. Our measured optical band gap values of Ga2O3Dy3 and Ga2O3Dy3 M3 thin lms for the as-deposited and annealed lms are shown in Table 1. In general the band gap values decrease slightly with the doping and co-doping of the Ga2O3 lms. These values are too large to absorb and utilize visible light. It has been reported that incorporation of metal ions into the Ga2O3 thin lms 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 signicant changes in the values of the band gaps because, our lms 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 mainly consists of narrow lines in the blue region (470500 nm) and yellow region (570600 nm). The two emissions have originated from 4F9/2-6H15/2 and 4F9/2-6H13/2 transitions of Dy3 [25]. The 4F9/2-6H13/2 transition is hypersensitive and its intensity strongly depends on the host, in contrast to a less sensitive 4 F9/2-6H15/2 transition of Dy3 [26]. Our experimental results in Fig. 5 show PL from 450700 nm of all samples. No signals associated to undoped Ga2O3 thin lms. However for the lms doped with Dy3 (Ga2O3Dy3 ) 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 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 transition of Dy3 ion. On the other hand, for the co-doped lms

(Ga2O3Dy3 Cr3 and Ga2O3Dy3 Co3 ), it is possible to observe the same spectral pattern of the signals but their intensities decreased signicantly. There are no signals that can be assigned to Cr3 or Co3 ions. It should be noted that both as-deposited and annealed 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 developing a nano-sized luminescent material activated by RE elements because absorption and emission properties of intra-4f-congurational 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 lms, there was no signicant 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 annealing samples at high temperature decrease the excitation efciency and the corresponding emission due to the loss of oxygen weakly absorbed on the surface of the lms that can act as a bridge to enhance the bonding state of activator (Dy3 ions) with OGa 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 inuences PL properties of the Ga2O3Dy3 lms; in this case the concentration of 10 mol% of co-dopant decreases the PL properties of the Ga2O3Dy3 lms; the presence of Co3 or Cr3 ions at 10 mol% may act as PL killers due to the energy transfer from excited Dy3 to Co3 or Cr3 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 prepared by the solgel method have shown that on co-doping with different amounts of Br [30] or Bi3 or Zr4 [31] the PL intensities decrease when the co-dopant concentration is 41 mol%. Based on the results obtained by other authors [3032], similar to those obtained in this work, we proposed a model of energy transfer to explain why the co-doping in the lms causes a reduction in the PL emissions of Dy3 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) 11701174

575 nm

80000
500 nm

60000 50000
500 nm 575 nm

70000 60000
Intensity (a.u.)

Intensity (a. u.)

622 nm

594 nm 605 nm

50000 40000 30000 20000 10000 0 450 500

(4)

40000 30000 20000 10000 0 450

652 nm

(3) (2) (1)

605 nm

(4)

594 nm

622 nm 652 nm

(3) (2)

(1)

550 600 Wavelength (nm)

650

700

500

550 600 Wavelength (nm)

650

700

Fig. 5. PL spectra of (a) as-deposited and (b) annealed lms at 800 1C of the samples: (1) Ga2O3; (2) Ga2O3Dy3 Co3 ; (3) Ga2O3Dy3 Cr3 and (4) Ga2O3Dy3 thin lms.

Acknowledgments The authors are grateful to the nancial support of the FONDECYT (National Fund for Scientic and Technological Development), Chile, Grant no. 1100045 and Direccion de Investigacion de la U. del Bo-Bo, DIUBB proyect. Grant no. 092509 3/R. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] Fig. 6. A simple model illustrating the emission process in Ga2O3Dy3 thin lms and the energy transfer from Ga2O3Dy3 M3 thin lms (M Cr or Co). [11] [12] G. Sinha, A. Patra, Chem. Phys. Lett. 473 (2009) 151. P. Marie, X. Portier, J. Cardin, Phys. Status Solidi A 205 (2008) 1943. S. Fujihara, Y. Shibata, J. Lumin. 121 (2006) 470. Z. Ji, J. Du, J. Fan, W. Wang, Opt. Mater. 28 (2006) 415. G. Sinha, K. Adhikary, S. Chaudhuri, Opt. Mater. 29 (2007) 718. Q. Xu, S. Zhang, Superlattices Microstruct. 44 (2008) 715. H. Woo Kim, N. Ho Kim, J. Alloys Compd. 389 (2005) 177. B. Marciniak, G.E. Buono-Core, J. Photochem. Photobiol. A: Chem. 52 (1990) 1. S. Giuffrida, G. Condorelli, L. Costanzo, I. Fragala, G. Ventimiglia, G. Vecchio, Chem. Mater. 16 (2004) 1260. 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. S. Giuffrida, L. Costanzo, G. Condorelli, G. Ventimiglia, I. Fragala, Inorg. Chim. Acta 358 (2005) 1873. C. Crisafulli, S. Scire, S. Giuffrida, G. Ventimiglia, R. Lo Nigro, Appl. Catal. A: Gen. 306 (2006) 51. L. Qin, C. Xue, Y. Duan, L. Shi, Physica B 404 (2009) 190. F. Shi, S. Zhang, C. Xue, J. Alloys Compd. 498 (2010) 77. J.C. Dupin, D. Gonbeau, P. Vinater, A. Levasseur, Phys. Chem. Chem. Phys. 2 (2000) 1319. M. Salavati-Niasari, J. Javidi, F. Davar, A. Amini Fazl, J. Alloys Compd. 503 (2010) 500. A.K. Bakshi, S.N. Jha, L. Olivi, D.M. Phase, R.K. Kher, D. Bhattacharyya, Nucl. Instrum. Methods Phys. Res. B 264 (2007) 109. s% _ _ _ S. Surviliene, V. Jasulaitiene, A. Ce uniene, A. Lisowska-Oleksiak, Solid State Ionics 179 (2008) 222. M.F. Al-Kuhaili, S.M.A. Durrani, Opt. Mater. 29 (2007) 709. A. Gulino, I. Fragala, Inorg. Chim. Acta 358 (2005) 4466. A. Avila, G.E. Barrera, C.L. Huerta, A.S. Muhl, Sol. Energy Mater. Sol. Cells 82 (2004) 269. M. Hellwig, Ke Xu, D. Barreca, A. Gasparotto, M. Winter, E. Tondello, R. Fischer, A. Devi, Eur. J. Inorg. Chem. (2009) 1110. G. Sinha, K. Adhikary, S. Chaudhuri, J. Cryst. Growth 276 (2005) 204. S. Chang, R. Doong, J. Phys. Chem. B 108 (2004) 18098. L.A. Diaz-Torres, E. De la Rosa, P. Salas, V.H. Romero, C. Angeles-Chavez, J. Solid State Chem. 181 (2008) 75. J. Pisarska, Opt. Mater. 31 (2009) 1784. S.K. Pillai, L.M. Sikhwivhilu, T.K. Hillie, Mater. Chem. Phys. 120 (2010) 619. G. Cabello, L. Lillo, C. Caro, B. Chornik, M.A. Soto, R. del Ro, M. Tejos, J. Phys. Chem. Solids. 71 (2010) 1367. G. Cabello, L. Lillo, C. Caro, G.E. Buono-Core, B. Chornik, M.A. Soto, J. NonCryst. Solids 354 (2008) 3919. C. Gao, H. Song, L. Hu, G. Pan, R. Qin, F. Wang, Q. Dai, L. Fan, L. Liu, H. Liu, J. Lumin. 128 (2008) 559. L. Hu, H. Song, G. Pan, B. Yan, R. Qin, Q. Dai, L. Fan, S. Li, X. Bai, J. Lumin. 127 (2007) 371. K.L. Frindell, M.H. Bartl, J. Solid State Chem. 172 (2003) 81.

(2) the electrons move freely in the CB and nally relaxes to the donor band (oxygen vacancies) or directly to 4F9/2 excited state level of Dy3 ; (3) the emission process occurs due to the transitions from the excited state 4F9/2 to the ground levels of 6 H15/2, 6H13/2 and 6H11/2 from Dy3 . These emission processes are reduced by (4) the presence of defects caused by co-doping of Cr3 or Co3 that produces the non-radiative energy transfer from the excited state of Dy3 to defects of the transition metals, leading to the decrease of emission intensity (5) and process of non-radiative transitions of transition metal (M).

[13] [14] [15] [16] [17] [18] [19] [20] [21] [22]

4. Conclusions The Ga2O3Dy3 Co3 and Ga2O3Dy3 Cr3 thin lms, were successfully prepared by a simple photochemical method. The compositional and structural characterization of the samples using XPS and XRD, respectively, revealed the Ga2O3 formation for the host material and Dy(III), Cr(III) or Co(III) as activators and the amorphous structure of the lms. The emission spectra of the Dy3 doped samples showed characteristic 4F9/2-6HJ (J 15/2, 13/2 and 11/2) transitions, but these emissions decreased with the co-doped lms. A study of decay times or decay processes of PL is necessary to verify the proposed mechanism in the present preliminary study.

[23] [24] [25] [26] [27] [28] [29] [30] [31] [32]