Chemical Physics Letters 397 (2004) 447450 www.elsevier.

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Strong erbium luminescence in the near-infrared telecommunication window

Rik Van Deun, Peter Nockemann, Christiane Go rller-Walrand, Koen Binnemans
Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium Received 9 August 2004; in nal form 2 September 2004

Abstract A new type of near-infrared emitting rare-earth complex has been synthesised, consisting of three bis(peruoroalkylsulfonyl)imide ligands and one 1,10-phenanthroline molecule. The chelate rings formed by the rare-earth ion and the bidentate ligands do not contain any carbon atoms and can hence be considered as inorganic chelate rings. The absence of CH stretching vibration modes in the rst coordination sphere of the rare-earth ion and the presence of a light-harvesting moiety (1,10-phenanthroline) bound to the rare-earth ion result in a complex that can be eciently excited and exhibits intense near-infrared luminescence. 2004 Elsevier B.V. All rights reserved.

1. Introduction The increasing demand for high speed information transfer is driving the switch from electrical to optical communications systems. Amplication of telecommunication signals is currently achieved by erbium-doped glass bre ampliers, that are based on the infrared photoluminescence of erbium(III) around 1550 nm (third telecommunication window) [1]. These bres are expensive and only low doping concentrations can be achieved. An erbium-doped polymer material could provide a lower cost, more versatile system [2,3]. However, the presently known luminescent inorganic erbium compounds or glasses are not compatible with polymeric matrices, due to their very low solubility in a polymer matrix and the diculties to disperse them in a polymer. On the other hand, erbium coordination compounds can show luminescence and are compatible with polymers [411]. The near-infrared photoluminescence of trivalent erbium ions is due to the 4I13/2 ! 4I15/2 transition,
Corresponding author. Fax: +32 16 32 79 92. E-mail address: Koen.Binnemans@chem.kuleuven.ac.be Binnemans).
*

(K.

with the emission maximum located around 1550 nm (i.e., 6450 cm1). Because of the relatively small energy gap between the excited state 4I13/2 and the ground state 4I15/2, the excited state is eciently quenched by the vibronic coupling with high energy OH, NH or CH stretching vibrations in the neighbourhood of the Er3+ ion. Hasegawa et al. [7] made neodymium(III) complexes of bis(peruoroalkylsulfonyl)imide ligands that showed near-infrared luminescence. The interesting feature of these compounds is not only the presence of the peruoroalkyl chains, but also the fact that no CH bonds are present in the chelate rings formed by the Nd3+ ion and the bidentate ligands. The six-membered inorganic chelate rings are formed by one neodymium atom, two oxygen atoms, two sulphur atoms and one nitrogen atom. Because the bis(peruoroalkylsulfonyl)imide ligands do not absorb light in the ultraviolet and visible part of the spectrum, the excited states of the lanthanide ion cannot be populated by energy transfer from an excited ligand, but only via direct excitation of the 4f-levels. Because the molar absorptivities of the 4f4f transitions are small, not much light can be absorbed, and therefore the luminescence intensities will be low.

0009-2614/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2004.09.011

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Here, we report the very intense near-infrared luminescence of a ternary erbium complex with inorganic chelate rings, consisting of three bis(peruoroalkylsulfonyl)imide ligands and one 1,10-phenanthroline molecule. The 1,10-phenanthroline group acts as a light-harvesting moiety and the excitation energy is transferred to the erbium ion. The erbium complex can be applied in polymeric erbium-doped optical ampliers, planar waveguides or infrared OLEDs.

and a Hamamatsu R5509-72 NIR-photomultiplier. The erbium spectra were measured by dispersing microcrystals into KBr pellets.

3. Results and discussion We extended the scope of the bis(peruoroalkylsulfonyl)imide lanthanide complexes reported by Hasegawa et al. [7] by forming Lewis base adducts of the tris complexes with 1,10-phenanthroline, in analogy with the 1,10-phenanthroline adducts of the tris (b-diketonato)lanthanide(III) complexes. Here, this approach is illustrated for tris[bis(peruorooctylsulfonyl)imide](1,10-phenanthroline)erbium(III), [Er(pos)3(phen)], see Fig. 1. The function of 1,10-phenanthroline is to saturate the coordination sphere of the Er3+ ion and to harvest excitation light that can be transferred to the excited states of the Er3+ ion. Upon direct excitation of the Er3+ ion in the 4f11 manifold at 520 nm (population of the 2 H11/2 level), a weak near-infrared photoluminescence signal centered around 1520 nm was observed at room temperature. This signal corresponds to the transition of the rst excited state (4I13/2) to the ground state (4I15/2) of the Er3+ ion. When the excitation wavelength was changed to 333 nm, the intensity of the photoluminescence signal increased dramatically by a factor of more than 20 (Fig. 2). This excitation wavelength corresponds to the absorption maximum of the 1,10-phenanthroline ligand. The wavelength of the maximum in the absorption spectrum of the complex corresponds remarkedly well to that of the maximum intensity seen in the excitation spectrum. In fact, both absorption and excitation spectra are very similar. This indicates that a very ecient energy transfer occurs between the phenanthroline unit and the bis(peruorooctylsulfonyl)imide erbium moiety. This behavior is not trivial. When an analogous b-diketonate complex [Er(dbm)3 (phen)] (with dbm = dibenzoylmethanate) was examined, the eect of changing the excitation wavelength from the erbium band at 520 nm to the phenanthroline band at 325 nm only resulted in a 2.5-fold increase of the luminescence output. In Fig. 3, the excitation spectrum of the [Er(pos)3(phen)] complex is given, whereas the excitation spectrum of the comparable [Er(dbm)3(phen)]

2. Experimental 2.1. Synthesis of the erbium complex [Er(pos)3(phen)] The potassium salt of the ligand bis(heptadecauorooctylsulfonyl)imide was synthesized according to the literature procedure [12], which involves the reaction of heptadecauorosulfonyl uoride with triuoracetamide in the presence of potassium carbonate as the base. A solution of ErCl3 6H2O (0.124 g; 0.33 mmol) in 20 mL of absolute ethanol was added dropwise to a solution of K(N(SO2C8F17)2) (1.00 g; 0.98 mmol) in 50 mL of absolute ethanol. After stirring for 30 min, the mixture was allowed to cool to room temperature over a period of 1 h and was kept for an additional hour at 4 C. Subsequently the precipitated potassium chloride was ltered o. An equimolar amount of 1,10-phenanthroline monohydrate (0.0648 g; 0.33 mmol) dissolved in 20 mL of absolute ethanol was added to the solution and the mixture was heated at reux for 3 h. After cooling the solution to room temperature, 50 mL of water was added and the ethanol was evaporated under reduced pressure. The resulting solid was ltered o, washed with water and n-hexane. The solid was dissolved in acetone, ltered again, and the acetone was removed under reduced pressure. The compound was dried in vacuo rst at 50 C for 12 h, and then at 105 C for 12 h (yield: 85%). M.p. 315 C, CHN-analysis results for C60H8F102N5O12S6Er (Mw: 3288.22), Found: (Calcd.): C: 21.53 (21.92), H: 0.13 (0.25), N: 1.78 (2.13)%. IR (KBr, cm1): 1350 (m, S@O), 1202, 1249 (s, CF), 1150 (s, SO). 2.2. Instrumentation Elemental analyses (CHN) were performed on a CEInstrument EA-1110 elemental analyser. The infrared spectra have been measured on a Bruker IFS66 spectrometer, by use of the KBr pellet method. The melting point has been measured by DSC (MettlerToledo DSC module 822e). The near-infraed luminescence and the luminescence decay curves have been recorded on an Edinburgh Instruments FS-920P spectrouorimeter equipped with a xenon arc lamp (450 W), a Nd:YAG pumped dye-laser, a double excitation monochromator,

C8F17 N C8F17

O S S O 3 O Er O N N

Fig. 1. Chemical structure of the erbium compound [Er(pos)3(phen)].

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Fig. 2. Near-infrared luminescence spectrum of the erbium compound [Er(pos)3(phen)] at room temperature, upon excitation in the absorption band of 1,10-phenanthroline at 333 nm (solid line). The luminescence spectrum observed upon excitation in the erbium absorption band at 520 nm is shown for the sake of comparison (dashed line).

Fig. 4. Excitation spectrum of [Er(dbm)3(phen)] in a KBr pellet at room temperature.

Fig. 5. Compared emission spectra of [Er(dbm)3(phen)] in a KBr pellet, upon excitation in the phenanthroline unit (325 nm, solid line) and in the erbium 2H11/2 level (520 nm, dashed line). The spectra were recorded at room temperature. Fig. 3. Excitation spectrum of [Er(pos)3(phen)] in a KBr pellet at room temperature.

complex can be seen in Fig. 4. The emission spectra of the latter complex (excited at 325 and 520 nm) are displayed in Fig. 5. It should be noted that in the [Er(dbm)3(phen)] complex the excitation light is not only absorbed by the phenanthroline ligand, but also by the b-diketonate ligands. Selective excitation of the phenanthroline moiety is not possible, because of overlap of the absorption bands of the two chromophores. The unusual strong increase of the luminescence signal upon addition of 1,10-phenanthroline to the uorinated bis(peruorooctylsulfonyl)imide complex (as compared to the b-diketonate complex with non-uorinated ligands) may be due to the stronger binding constant of the phenanthroline moiety to the bis(peruoro-

octylsulfonyl)imide complex. This is reasonable to expect, because the uorinated ligands have a strong electron-withdrawing eect on the erbium(III) ion and 1,10phenanthroline is a good electron donor. The ne structure in the emission spectrum in Fig. 2 is due to transitions between the crystal-eld levels of the 4I13/2 and 4I15/2 manifolds. The presence of crystal-eld ne structure is an indication that the Er3+ ion occupies well-dened crystallographic sites in [Er(pos)3(phen)]. This hypothesis is supported by the luminescence spectrum of the corresponding europium complex [Eu(pos)3(phen)], in which one clearly distinguishable peak was observed for the 5D0 ! 7F0 transition. This indicates the existence of a single crystallographic site. To enable a wide gain bandwidth for optical amplication, a broad emission band is

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desirable. The full-width at half-maximum (FWHM) of the 4I13/2 ! 4I15/2 transition in [Er(pos)3 (phen)] is 100 nm. This is an exceptional broad emission band for an erbium-doped material. For instance, Sloo et al. [3] observed a FWHM of 70 nm for a terphenyl-based acyclic erbium complex. 4. Conclusions In conclusion, we have shown that an impressive increase of the erbium-centered near-infrared luminescence intensity can be achieved by using 1,10-phenanthroline as the light-harvesting moiety in complexes with inorganic chelate rings. These chelate rings, consisting of bis(peruoroalkylsulfonyl)imides, contain no CH bonds which could be ecient quenchers of the nearinfrared luminescence, resulting in low loss of the absorbed energy. By using 1,10-phenanthroline, the amount of light that can be absorbed is several orders of magnitude higher than when exciting directly into the f-levels of the erbium ion. Moreover, the phenanthroline moiety has a good energetic match with the bis(peruoroalkylsulfonyl)imide erbium(III) system, in the sense that the energy absorbed by the phenanthroline is eciently transferred to the erbium(III) center. This can be clearly illustrated by the excitation spectrum, which closely resembles the absorption spectrum of the same complex. This results in an increase in the luminescence intensity of more than 20 times compared to direct excitation in the Er3+ levels, which is unprecedented. This easily synthesisable system oers a wide range of possible modications, in order to increase the solubility in optical polymer materials, thus paving the way towards cheap and easily processable high intensity near-infrared emitting devices.

Acknowledgements This research was funded by the European community (Contract GROWTH No: GRD2-2000-30346 OPAMD), the K.U. Leuven (GOA 03/03) and the Fund for Scientic Research, Flanders (G.0117.03). RVD and KB are postdoctoral fellows of the Fund for Scientic Research, Flanders (Belgium) (F.W.O. -Vlaanderen). CHN microanalyses were done by P. Bloemen.

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