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Journal of Luminescence 122123 (2007) 125127 www.elsevier.com/locate/jlumin

Up-conversion properties of Yb3+, Ho3+: Lu2O3 sintered ceramic

Liqiong An, Jian Zhang, Min Liu, Shiwei Wang
Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, PR China Available online 10 March 2006

Abstract The up-conversion spectra of sintered ceramic Lu1.896Yb0.1Ho0.004O3 are reported. The dominant green, weak red and infrared emissions are observed excited by 980 nm diode laser. The ultra-violet and blue up-conversion emissions are also detected in the range 381394 and 409428 nm. Power study reveals that the emitting levels are populated via two-photon/three-photon excited-state absorption and energy transfer up-conversion process. r 2006 Elsevier B.V. All rights reserved.
Keywords: Up-conversion; Lu2O3; Sintered ceramic

1. Introduction There has been an increasing interest in up-conversion studies of rare-earth ions doped various materials including crystals, glasses, thin lms and ceramics due to the development of the high-power laser diodes and the requirement for short wavelength emitting solid state lasers. Ho3+ is a suitable active ion for its abundant energy levels with luminescence ranging from 400 to 3000 nm. The materials co-doped with Yb3+ and Ho3+ are especially interesting in up-conversion lasers that can be pumped with a commercial 980 nm diode laser by means of the energy transfer (ET) from Yb3+ to Ho3+ [13]. Lu2O3, as a sesquioxide isostructural to Y2O3, has received great attention for its potential application in scintillators, lasers and phosphors for lighting and displays [4,5]. It possesses relatively low phonon energy (about 600 cm1) [6] and its powders can be sintered into transparent [7], which makes it additionally attractive for practical applications. In this paper, the up-conversion properties of Lu2O3 sintered ceramic co-doped with Yb3+ and Ho3+ are investigated.

2. Experimental Lu1.896Yb0.1Ho0.004O3 powders were prepared via a reverse-strike co-precipitation method. Details of synthesis have been described in a previous work [8]. The asprepared powders were cold pressed under 30 MPa into plates with 12-mm diameter, and then were sintered at 1850 1C for 3 h in owing H2 atmosphere. Therefore, the translucent ceramics were obtained. Up-conversion luminescent spectra of sintered ceramic were recorded at room temperature by a spectrouorometer (Fluorolog-3, Jobin Yvon, Edision, USA) equipped with Hamamatsu R928 photomultiplier. A 980 nm continuous wave diode laser was used as excitation source. All the emission spectra were corrected for the setup characteristic. 3. Results and discussion On excitation of 980 nm diode laser, the up-conversion luminescence from the sample appeared as a dazzling green spot and could be clearly seen by naked eyes even when the excitation power was as low as 10 mW. Fig. 1 shows the typical room temperature up-conversion spectra of sintered samples. The green emission centered at 548 nm dominates the whole spectrum corresponding to the multiplets 5F4, 5 S2-5I8 transition of Ho3+ ions. The red emission was

Corresponding author. Tel.: +86 21 52414320; fax: +86 21 52413903.

E-mail address: Swwang51@mail.sic.ac.cn (S. Wang). 0022-2313/$ - see front matter r 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jlumin.2006.01.118

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Fig. 1. Up-conversion spectra of sintered ceramic Lu1.896Yb0.1Ho0.004O3 excited at 980 nm. Inset: details of up-conversion emissions in the range of 350510 nm.

detected around 667 nm associated with the 5F5-5I8 transition. The infrared emission centered around 753 nm was observed, which is assigned to the 5F4, 5S2-5I7 transition. Furthermore, the ultra-violet and blue upconversion emissions can also be measured. The ultraviolet emissions in the ranges 381394 nm and 409428 nm are assigned to the 5G4-5I8 and 5G5-5I8 transitions, respectively. The blue emission between 473 and 500 nm is from the 5F3-5I8 transition. The up-conversion emission intensities of the visible signals against the power of diode laser were examined and the lnln plot is shown in Fig. 2. The up-conversion emission intensity Iup depends upon the pump power according to Iupp(Ip)n, where n is the number of pump photons involved in the up-conversion process [9]. It has a quadratic behavior (slope $2) for the green and infrared emissions and a nearly cubic power law (slope $3) for ultra-violet and blue emissions. It is deduced that two and three pump photons were involved in the process of upconversion emissions. It is well-known that Yb3+ ions have large absorption bands around 1000 nm, which match the wavelength of 980 nm diode laser very well. So in our measurement the possible up-conversion mechanism for the resulting emission bands is energy transfer for the sensitizing effect of Yb3+ [2,10]. Fig. 3 shows the partial energy level diagram with the energy transfer from Yb3+ to Ho3+. The 5F4, 5S2 levels can be populated by two successive energy transfers (SET) from Yb3+ ions [2] and excited state absorption (ESA) after phonon-assisted energy transfer [11]. The Ho3+ ions in the 5F4, 5S2 levels can be excited to upper excited state by successive energy transfer and excited state

Fig. 2. Lnln plots of up-conversion emissions intensity as a function of the excitation power of the diode laser.

absorption and then relaxed to lower excited states 5G4, 5 G5 and 5F3 by multiphonon relaxation process. The 5F3 level can also be populated by stepwise phonon-assisted two-photon absorption followed by multiphonon relaxation [12]. A nonresonant pump photon at 980 nm promotes Ho3+ ions population from the 5I8 ground state to the 5I5 level by means of a phonon-assisted absorption process. The 5F3 level can be excited by a second pump photon nonresonantly with excess energy (approximately 500 cm1) transferred to the host lattice. Therefore, we can observe the ultra-violet and relatively intense blue

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sorption and energy transfer up-conversion process. An assisted-phonon energy transfer mechanism was determined to play an important role in the up-conversion process. Acknowledgments This work was nancially supported by the Chinese National Science Foundation (50372075) and Shanghai Light-Tech Project (036105021). References
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Fig. 3. The partial energy level diagram of Lu1.896Yb0.1Ho0.004O3 excited by 980 nm diode laser.

emissions. The 5F5 level may be populated by the relaxation process from the 5F4, 5S2 levels and then the red emission was observed. 4. Conclusions The dominant green, weak red and infrared, ultra-violet and blue up-conversion emissions were observed in sintered ceramic Lu1.896Yb0.1Ho0.004O3 under excitation of 980 nm. The dependence of the up-conversion intensity upon the exciting power reveals that the emitting levels are populated via two-photon/three-photon excited-state ab-