Thin Film Deposition of Tb<sub>3</sub>Al<sub>5</sub>O<sub>12</sub>:Ce by Pulsed Laser Ablation and Effects of Low-temperature Post-annealing
Thin Film Deposition of Tb3Al5O12:Ce by Pulsed Laser Ablation and Effects of Low-temperature Post-annealing
Journal of the Optical Society of Korea. 2012. Mar, 16(1): 76-79
Copyright ©2012, Optical Society of Korea
  • Received : January 06, 2012
  • Accepted : January 30, 2012
  • Published : March 25, 2012
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About the Authors
Kang Min Kim
The Institute of Scientific and Industrial Research, Osaka University, Ibaraki, Osaka 567-0047, Japan
Jun Ho Chung
Department of Materials Science and Engineering, Hanyang University, Seongdong-gu, Seoul 133-791, Korea

Tb 3 Al 5 O 12 :Ce (TAG:Ce) thin films were successfully deposited by a pulsed laser ablation method on a quartz substrate, and low-temperature post-annealing effects on luminescent properties were investigated in detail. TAG:Ce thin films were analyzed by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The as-deposited films were amorphous, and post-annealing above 700℃ was required for crystallization. The post-annealed TAG:Ce thin films showed strong and broad emission bands around 542 nm and excitations at 451 nm, which all corresponded to transitions between the 4f ground level to the 5 d 1 excited levels of Ce ion.
With the prospect of a highly efficient light source, the light emitting diodes (LEDs) market will have enormous growth, and white LEDs will be a likely candidate for the replacement of the light bulb. A commercially available white LED based on phosphors has been produced by Nichia Co., which used a blue light-emitting gallium indium nitride (GaInN) chip coated with yellow Y 3 Al 5 O 12 :Ce (YAG:Ce) phosphor [1 - 3] . However, the color temperature of YAG:Ce phosphor used for phosphor-converting LEDs is too high to use in warm white LEDs application due to lack of red component [4] .
As an alternative for YAG:Ce, Tb3Al5O12:Ce (TAG:Ce) has emerged as an excellent phosphor material for white LEDs, because the TAG:Ce is capable of absorbing radiation in the range from near UV to blue, and emitting a broad spectrum of visible light in the range from approximately 490 nm to approximately 770 nm [5] . It is well known that when compared with YAG:Ce, the spectrum of the TAG:Ce is slightly shifted to red range, which is advantageous to resolve the problem of the high temperature of YAG:Ce LEDs [6] .
In general, the phosphor-converting white LEDs are embedded in organic resins. However, there are several problems in these types of white LEDs, including the large difference of refractive index between phosphors and organic resins which will lead to a high amount of light scattering, and the poor heat-resistance which will lead to the degradation of luminous intensity with the change of color index [7] . In order to solve these problems, new types of white LEDs, for example, using glass ceramic or sintered ceramic phosphors have been developed [8 , 9] .
In this study, TAG:Ce luminescent thin films were deposited using a pulsed laser ablation (PLA) technique as a new type of white LED. The PLA offers many advantages over other thin film deposition techniques such as chemical vapor deposition (CVD) or physical vapor deposition (PVD) [10] . Unlike the CVD process in which complicated precursors are used as starting materials, PLA uses a pre-sintered solid target from which the thin film is deposited. And, film growing rate can be easily controlled by varying the laser parameters, background gas pressure and distance from substrate to target [11] . The main feature of the PLA method is the excellent stoichiometric transfer from the multi-compositional solid target to the thin film with homogeneity and uniformity over the designated depositing areas [12] .
Phosphors in powder form usually yield higher luminescence than that of thin film types, mainly due to lower loss of light from total internal reflections. However, by modifying surface shape and morphology of the films, several significant improvements in increasing light output have been reported [13] . Comparing to powder typed phosphor, thin film typed phosphor can be more conveniently integrated with LEDs, therefore, it can be a better processing method for fabricating white light-emitting systems [14] . In this report, the crystallographic evolution, surface morphology, compositional qualities, and photoluminescence (PL) characteristics of the TAG:Ce thin films deposited by the PLA technique are discussed. Moreover, low-temperature post-annealing effects on PL properties are investigated in detail.
The starting TAG:Ce powder was synthesized by a citrate complex method with a optimum Ce doping concentration of 0.8 mol% [5] . A bulk target was prepared by compressing the prepared TAG:Ce powder under a uni-axial pressure of 300 MPa and then sintering at 1500℃ for 3 hrs. XRD measurement showed that the target had a single phase consistent with reported value (JCPDS 76-0111) as shown in inset of Fig. 1 . An Nd-YAG laser (wavelength = 355 nm) was used for the ablation. The repetition rate and pulse width of the laser were 10 Hz and 7 ns, respectively. The laser energy was 200 mJ/pulse and focused on a target rotating at 30 rpm. The quartz glass substrates were
Lager Image
XRD patterns of (a) JCPDS data for TAG crystal, (b) as-deposited TAG:Ce thin film and TAG:Ce thin film post-annealed at (c) 700 and (d) 800℃ for 2 hrs, respectively.
placed at an off-axial position with respect to the target in order to avoid large-sized particulate deposition [10 , 12] . The working pressure of background Ar gas during laser ablation was 100 Pa. All deposition processes were carried out at room temperature without substrate heating. Subsequently, the as-deposited samples were post-annealed at various temperatures from 600 to 800℃ in ambient atmosphere.
Phase identification was conducted with an X-ray diffractometer (XRD, Rigaku, RAD-C). The surface morphology of the deposited films was observed using a field-emission scanning electron microscope (FE-SEM, Hitachi S-4800, Japan). The surface composition and chemical bonding analysis were performed by X-ray photoelectron spectroscopy (XPS, PHI 5600 ci, USA) with a monochromated Al source (1486.5 eV, 100W). The binding energy values were calibrated with the C 1 s line of adventitious carbon at 284.5 eV. Luminescent properties of the TAG:Ce thin films were measured by a spectrofluorometer (Fluorolog Tau-3, Horiba, USA) in a room temperature using a xenon lamp as an excitation source. The excitation wavelength used for measuring PL emission was 450 nm, and the excitation spectra were measured at emission maxima.
Figure 1 shows XRD patterns of (a) JCPDS data for TAG crystal, (b) as-deposited TAG:Ce thin film and TAG:Ce thin film post-annealed at (c) 700 and (d) 800℃ for 2 hrs, respectively. The as-deposited films were amorphous in nature, and did not represent any crystalline peaks. Post-annealing less than 700℃ did not effectively crystallize the thin film. The thin films started to crystallize when annealed at 700℃ for 2 hrs as shown in (c). However, an intermediate TaAlO 3 (terbium aluminum perovskite, TAP) phase coexisted with the TAG phase. Completely crystallized pure TAG phase was obtained after post-annealing at 800℃ for 2 hrs as shown in (d). This post-annealing temperature is somewhat similar to that of citrate-complex derived TAG:Ce powders [5] , and significantly lower than that of the conventional solid-state reaction process [15] .
Figure 2 shows the surface morphologies of the TAG:Ce films (a) as-deposited and (b) post-annealed at 800℃ for 2 hrs. The surface microstructure of the TAG:Ce thin films deposited by PLA was affected by a post-annealing process. Indeed, the surface of the as-deposited TAG:Ce thin film exhibits a smooth morphology without particular features. However, after post-annealing treatment at 800℃ for 2 hrs, the surface became rougher resulting from grain growth and formation of particulates as shown in (b). The inset of (b) shows a cross-sectional view of the sample of thickness about 250 nm after annealing at 800℃ for 2 hrs.
The surface composition of the TAG:Ce thin film post-annealed at 800℃ for 2 hrs was analyzed using XPS. Figure 3 (a-d) presents the high resolution XPS spectra of the (a) Tb 4d, (b) Al 2p, (c) O 1s, and (d) Ce 3d. The
Lager Image
SEM images of TAG:Ce thin films (a) as-deposited and (b) post-annealed at 800℃ for 2 hrs. The inset of (b) show cross-sectional view of thin film post-annealed at 800℃ for 2 hrs.
Lager Image
XPS spectra of the (a) Tb 4d, (b) Al 2p, (c) O 1s, and (d) Ce 3d region in TAG:Ce thin film post-annealed at 800℃ for 2 hrs.
binding energies of the Tb, Al, O, and Ce were well in agreement with reported values [16] . The Ce 3d feature in (d) shows a complex structure consisting of Ce 3d 5/2 and Ce 3d 3/2 spin-orbit doublet around 885 and 904 eV, respecti-
Lager Image
Excitation and emission spectra of the (a) TAG:Ce thin films post-annealed at 700 and 800℃ for 2 hrs. PL spectra of bulk TAG:Ce are shown in (b) for comparison.
respectively, which is a characteristic property of the Ce 3+ ion [17] .This spectral feature confirms that the chemical valence of Ce ions doped in the TAG:Ce thin film is trivalent. Moreover, a calculated chemical composition of Ce 3+ in the TAG:Ce film post-annealed at 800℃ for 2 hrs was 0.075, which corresponded well to the doping concentration of the bulk target (8 mol%).
Figure 4 (a) depicts the excitation and emission spectra of the TAG:Ce thin film post-annealed after PLA process. The PL spectra of the bulk target used for PLA are presented in (b) for comparison with those of the TAG:Ce thin films. As shown in Fig. 4 , both excitation and emission spectral shapes of the TAG:Ce thin films are almost identical to those of the target used for the PLA. The PL intensity of the as-deposited film (not shown) was almost two orders lower than those of the post-annealed thin films. The emission intensity of the TAG:Ce thin film post-annealed at 700℃ for 2 hrs was about 10% of the bulk target. This low PL intensity may originate from incom-plete crystallization and an intermediate TAP phase. However, enhancement of the emission spectrum up to 30% of the bulk target was observed in the sample post- annealed at 800℃ for 2 hrs. This result indicates that low-temperature post-annealing process can remarkably enhance the emission intensity of the TAG:Ce thin film deposited by PLA in room temperature. The PL excitation spectrum of the post-annealed TAG:Ce thin films showed two bands peaking at 335 (weak) and 450 nm (strong) due to the transitions from 4f 1 ground state to higher level of 5d 1 configuration. The broad emission spectra centered at 542 nm correspond to the well-known transition from the lowest 5d1 (2D) configuration to the unresolved ground states 4f1 ( 2 F 5/2,7/2 )of the Ce ion in TAG crystal [18] .
In summary, Tb 3 Al 5 O 12 :Ce (TAG:Ce) luminescent thin films were successfully deposited by pulsed laser ablation (PLA) with a low-temperature post-annealing process. XPS analysis showed that the PLA process preserved the chemical bonding property of the target that was effectively transferred to the deposited films after post-annealing at 800℃ for 2 hrs in ambient conditions. Furthermore, the luminescent property was recovered by the low-temperature post-annealing process. The strong emission band around 542 nm was obtained by exciting the 5d1 energy levels of the Ce ion at 450 nm. It is considered that the TAG:Ce thin films deposited by PLA can be a promising component for new-typed white LEDs.
This work was supported by the Regional Innovation Center (RIC) Program conducted by the Ministry of Knowledge Economy of the Korean Government.
Nakamura S (1997) “Present performance of InGaN based blue/green/yellow LEDs” Proc. SPIE 3002 26 - 35
Ryu H.-Y , Kim D.-H (2010) “High-brightness phosphor-conversion white light source using InGaN blue laser diode” J. Opt. Soc. Korea 14 415 - 419    DOI : 10.3807/JOSK.2010.14.4.415
Son C. G , Yi J. H , Gwag J. S , Kwon J. H , Park G (2011) “Improvement of color and luminance uniformity of the edge-lit backlight using the RGB LEDs” J. Opt. Soc. Korea 15 272 - 277    DOI : 10.3807/JOSK.2011.15.3.272
Ye S , Xiao F , Pan Y. X , Ma Y. Y , Zhang Q. Y (2010) “Phosphors in phosphor-converted white lihgt-emitting diodes: recent advances in materials techniques and properties” Mat. Sci. Eng. R 71 1 - 34    DOI : 10.1016/j.mser.2010.07.001
Kim K. M , Ryu J. H , Mhin S. W , Park G. S , Shim K. B C. C. “Luminescence of nanocrystalline Tb3Al5O12::Ce3+phosphors synthesized by nitrate-citrate gel combustion method” J. Electrochem. Soc. (2008) J293 - J296    DOI : 10.1149/1.2966689
Chiang C. C , Tsai M. S , Hon M. H (2007) “Synthesis and photoluminescent properties of Ce3+doped terbium aluminum garnet phosphors” J. Alloy Compd. 431 298 - 302    DOI : 10.1016/j.jallcom.2006.05.068
Cui Z , Ye R , Hua Y , Deng D , Zhao S , Li C , Xu S (2011) “Spectral analysis of a novel Eu2+activated SiO2-BaO glass ceramics phosphor under UV-LED excitation” J. Non-Cryst. Solids 357 2298 - 2301    DOI : 10.1016/j.jnoncrysol.2010.11.064
Nishiura S , Tanabe S , Fujioka K , Fujimoto Y (2002) “Properties of transparent Ce:YAG ceramic phosphor for white LED” Opt. Mater. 33 258 - 271    DOI : 10.1016/j.optmat.2010.09.009
Bechtel H , Schmidt P , Busselt W , Schreinemacher B. S (2008) “Lumiramic: a new phosphor technology for high performance solid state light source” Proc. SPIE 7058 70580E1 - 10
Ryu J. H , Yoon J.-W , Shim K. B , Sasaki T , Koshizaki N (2006) “Room-temperature deposition of nanocrystalline CaWO4films by pulsed laser and their optical properties” J. Appl. Phys. 99 086103 -    DOI : 10.1063/1.2186370
Choe J. Y (2002) “Luminescence and compositional analysis of Y3Al5O12:Ce films fabricated by pulsed-laser deposition” Mat. Res. Innovat. 6 238 - 241    DOI : 10.1007/s10019-002-0204-4
Ryu J. H , Yoon J.-W , Shim K. B , Koshizaki N (2006) “Room-temperature deposition of nanocrystalline PbWO4thin films by pulsed laser ablation” Appl. Phys. A 84 181 - 185    DOI : 10.1007/s00339-006-3594-0
Nien Y.-T , Chen K.-M , Chen I.-G (2010) “Improved photoluminescence of Y3Al5O12:Ce nanoparticles by silica coating” J. Am. Ceram. Soc. 93 1688 - 1691
Narendran N , Gu Y , Freyssinier-Nova J. P , Zhu Y (2005) “Extracting phosphor-scattered photons to improve white LED efficiency” Phys. Status Solidi A 202 R60 - R62    DOI : 10.1002/pssa.200510015
Tsai M.-S , Liu G.-M , Chung S.-L (2008) “Fabrication of cerium active terbium aluminum garnet (TAG:Ce) phosphor powder via the solid-state reaction method” Mater. Res. Bull. 43 1218 - 1222    DOI : 10.1016/j.materresbull.2007.05.027
Kruczek M , Talik E , Sakowska H , Gała M , Świrkowicz M (2005) “X-ray photoelectron spectroscopy investigations of Y3Al5O12:Yb single crystal” Cryst. Res. Technol. 40 439 - 443    DOI : 10.1002/crat.200410363
Reddy B. M , Saikia P , Bharali P , Yamada Y , Kobayashi T , Muhler M , Grunert W (2008) “Structural characterization and catalytic activity of nanosized ceria-terbia solid solution” J. Phys. Chem. C 112 16393 - 16399    DOI : 10.1021/jp806131r
Mhin S. W , Ryu J. H , Kim K. M , Park G. S , Ryu H. W , Shim K. B , Sasaki T , Koshizaki N (2009) “Pulsed-laser-induced simple synthetic route for Tb3Al5O12:Ce3+colloidal nanocrystals and their luminescent properties” Nanoscale Res. Lett. 4 888 - 895    DOI : 10.1007/s11671-009-9331-9