Professional Documents
Culture Documents
A Simple Photochemical Method To Synthes
A Simple Photochemical Method To Synthes
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 Elsevier’s archiving and manuscript policies are
encouraged to visit:
http://www.elsevier.com/copyright
Author's personal copy
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.
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 1171
diffractometer. The X-ray source was Cu 40 kV/40 mA. X-ray was monitored by interferometry. The FT-IR spectrum of the
photoelectron spectra (XPS) were recorded on an XPS-Auger starting film was first obtained. The irradiation of the films was
Perkin Elmer electron spectrometer Model PHI 1257, which carried out at room temperature using two low-pressure Hg
included an ultra high vacuum chamber, a hemispherical electron lamps (6 W, Rayonet RPR—2537 A) in air, until the FT-IR spec-
energy analyzer and an X-ray source providing unfiltered Ka trum showed no evidence of the starting material. Prior to
radiation from its Al anode (hn ¼1486.6 eV). The pressure of the analysis, the chip was rinsed several times with dry acetone to
main spectrometer chamber during data acquisition was main- remove any organic products remaining on the surface. In order
tained at ca.10 7 Pa. The binding energy (BE) scale was calibrated to obtain films of a specific thickness, successive layers of the
using the peak of adventitious carbon, setting it to 284.6 eV. The precursors were deposited by spin-coating and irradiated as
accuracy of the BE scale was 70.1 eV. Solid state photolysis was above. This process was repeated several times until the desired
carried out at room temperature under a low-pressure Hg lamp thickness was achieved. Post-annealing was carried out under a
(l ¼254 nm) equipped with two 6 W tubes, in air. Progress of the continuous flow of synthetic air at 800 1C for 3 h in a program-
reactions was monitored by determining the FT-IR spectra at mable Lindberg tube furnace.
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 3. Results and discussion
silicon (1 0 0) wafers (1 1 cm2) obtained from Wafer World
Inc., Florida, USA. 3.1. Photochemistry of Ga(III) and Dy(III) b-diketonate complexes
Photoluminescense (PL) emission spectra measurements were
carried out in an Ocean Optics Model QE65000-FL spectrometer The photochemistry of metal b-diketonate complexes has been
with an L type setup. Excitation was done with a PX-2 pulsed widely investigated [8–10], because they absorb strongly at
Xenon lamp (220–750 nm), and the UV light passed through a readily accessible parts of the UV spectrum (250–400 nm). In
monochromator set to 254 nm. The measurements were done at general, the irradiation of these complexes with UV light
room temperature. (254 nm) leads to the photo-reduction of these complexes, upon
LMCT (ligand-to-metal charge transfer) excitation to form metals.
2.2. Preparation of amorphous thin films In this case no reports can be found in the literature concerning
Ga(acac)3 and Dy(thd)3 complexes. We therefore carried out
The precursors Ga(III), Co(III), Cr(III) acetylacetonate com- experiments to evaluate the photo-reactivity of these complexes
plexes and Dy tris(2,2,6,6-tetramethyl-3,5-heptanedionate) in solution as a film. When dichloromethane solutions of these
complex were purchased from Aldrich Chemical Company and complexes were photolyzed with 254 nm UV light, a complete
thin films were prepared by the following procedure: a silicon disappearance of the absorption bands of these complexes could
chip was placed on a spin coater and rotated at a speed of be observed after 300 min of irradiation (Fig. 1). The electronic
1500 RPM. A portion (0.1 ml) of a solution of the precursor spectra of Ga(III) and Dy(III) b-diketonate complexes exhibited
complex in CH2Cl2 was dispensed onto the silicon chip and bands at 285 and 275 nm, respectively. The observed absorption
allowed to spread. The motor was then stopped after 30 s and a bands have been assigned to the various electronic transitions. In
thin film of the complex remained on the chip. The quality of the dichloromethane diluted solutions, irradiation of the Ga(acac)3
films by optical microscopy was examined (500 magnification). complex at 254 nm provoked fast spectral changes consisting of
decreases of the absorption band at 285 nm and slight shift of the
2.3. Photolysis of complexes as films on Si (1 0 0) surfaces band at 274 nm, which is characteristic of the free 2,4-pentan-
dione ligand (Hacac) associated with a p–p* (HOMO-LUMO)
All photolysis experiments were conducted following the same transition [11,12], which also degrades (Fig. 1a).
procedure: a film of the complex was deposited on n-type Si On the other hand, the Dy(thd)3 complex exhibits a single
(1 0 0) by spin-coating from a CH2Cl2 solution. This resulted in band at 275 nm, attributable to ligand transition of a p–p*, the
the formation of a smooth, uniform coating on the chip. The break of hydrogen intraligand bond, present in the enol form of
quality (uniformity, defects, etc.) of the precursor films was the ligand, and the formation of two hydrogen intermolecular
determined by optical microscopy (500 ), while the thickness bonds with the solvent, giving an electronic situation similar to
2.0 2.0
1.8 t0 1.8
1.6 1.6 t0
1.4 1.4
Absorbance
1.2
Absorbance
1.2
1.0
1.0
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.0
0.0
250 275 300 325 350 375 400 250 275 300 325 350 375 400
Wavelength (nm) 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.
Author's personal copy
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
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 1173
100 100
(1)
90 90
(1) (2)
80 80
Transmittance (%)
Trasmittance (%)
(2) Ga O -Dy
40
30 (2) Ga O -Dy (1)
(3) Ga O -Dy -Cr 30 (3) Ga O -Dy -Cr
20 (4) Ga O -Dy -Co
20 (4) Ga O -Dy -Co
10
200 300 400 500 600 700 800 900 200 300 400 500 600 700 800 900
Wavelength (nm) 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.
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
References