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In addition to photoluminescence, pyrene molecules also

display electroluminescence (EL).[15] The electrical conductivity of the pyrene-embedded PPy nanoparticles was 3.5 S cm1.
In EL devices, a PPy conducting layer can be used as a good
hole-transporting layer (HTL). In general, EL devices doped
with PPy as the HTL yield higher luminance efficiencies and
lower turn-on voltages.[16] It seems that a pyrene-embedded
PPy nanoparticle layer could be utilized as a good HTL (owing to the conducting ability of PPy) and also as an emitting
layer (EML) due to the EL properties of pyrene. Pyrene-embedded PPy nanoparticles can therefore be called HTL/EML
nanohybrids. In addition, the emission color can be tuned by
introducing other organic dyes, such as rhodamine B (red)
and fluorescein (green).
In conclusion, photochromic dyeconducting polymer core
shell nanomaterials were fabricated using microemulsion
micelles as nanoreactors. PPy nanoparticles (713 nm in
diameter) embedded with a pyrene core were successfully
synthesized. As the pyrrole monomer polymerized, pyrene
molecules were phase-separated and gathered together toward the interior of the micelle. The adsorption state of pyrene was tunable over a wide range with a small amount of
pyrene, because of the nanosized reaction site of the micelles
and the packing constraint of pyrene crystal. The emission
colors of the nanohybrids were controllable from violet to
blue by changing the amount of embedded pyrene. Our methodology provides a facile and effective way for controlling the
adsorption state of organic dyes, and also presents a new concept in use of the HTL/EML nanohybrids in EL devices.

Experimental
Synthesis of Pyrene-Embedded PPy Nanoparticles: 3 g of decyltrimethylammonium bromide (DeTAB) was magnetically stirred in 40 mL of H2O at 3 C.
Pyrene, in quantities of 0.5, 3, 5, and 10 mg, was mixed into 1.0 g (14.9 mmol)
of pyrrole monomer. The mixture was added dropwise to the surfactant solution. FeCl3 (5.561 g, 34.3 mmol) was dissolved in a small amount of distilled
water and the solution was added to the reaction mixture. Chemical polymerization proceeded for 3 h at 3 C. The reaction product was moved to a separating funnel and excess methyl alcohol was added to remove the surfactant and
residual ferric chloride. A small amount of isooctane was added to promote the
precipitation of the PPy nanoparticles, owing to the enhanced hydrophobicity.
The upper solution containing surfactant and unreacted ferric chloride was discarded and the nanoparticle precipitate was dried in a vacuum oven at room
temperature. For comparison, pure PPy nanoparticles, without any embedded
pyrene, were also synthesized. For the photoluminescence experiments, pyrene
and pyrene-embedded PPy nanoparticles were dispersed in benzene and methyl
alcohol (spectrophotometric grade), respectively.
Instrumental Analysis: The TEM images and EDX data were taken using a
Philips CM-20 microscope coupled with an EDX facility. Emission spectra were
obtained with a Shimadzu RF-5301 PC spectrofluorophotometer. The excitation wavelength for the emission spectrum was 334 nm, which was the maximum absorption wavelength of pure pyrene dissolved in benzene. Infrared
spectra were recorded on a Bomem MB 100 FTIR spectrometer. NMR analysis
was performed with a Bruker Avance-500 machine. Elemental analysis was conducted with an EA1110 apparatus (CE Instruments).

[1]
[2]

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Received: January 4, 2003

Final version: March 7, 2003

a) A. P. Alivisatos, Science 1996, 271, 933. b) J. S. Yin, Z. L. Wang, Phys.

Rev. Lett. 1997, 79, 2570. c) F. Caruso, R. A. Caruso, H. Mhwald, Science
1998, 282, 1111.
E. A. Silinsh, Organic Molecular Crystals: Their Electronic States, Springer-Verlag, Berlin 1980.

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[3] J. K. Lee, W. K. Koh, W. S. Chae, Y. R. Kim, Chem. Commun. 2002, 138.

[4] a) D. Grosso, G. J. D. A. A. Soler-Illia, F. Babonneau, C. Sanchez, P. A.
Albouy, A. Brunet-Bruneau, A. R. Balkenende, Adv. Mater. 2001, 13,
1085. b) Y. K. Hwang, K. C. Lee, Y. U. Kwon, Chem. Commun. 2001,
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[5] H. Fu, B. H. Loo, D. Xiao, R. Xie, X. Ji, J. Yao, B. Zhang, L. Zhang, Angew. Chem. Int. Ed. 2002, 41, 962.
[6] Y. Matsuo, K. Hatase, Y. Sugie, Chem. Commun. 1999, 43.
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b) J. Jang, J. H. Oh, Chem. Commun. 2002, 2200.
[8] H. S. Nalwa, Handbook of Organic Conductive Molecules and Polymers,
Vol. 3, 1st ed., Wiley-VCH, Chichester, UK 1997, p. 38.
[9] M. Sengoku, S. Sawai, T. Ohno, Micron 2001, 32, 447.
[10] a) C. L. Winzor, D. C. Sundberg, Polymer 1992, 33, 3797. b) M. Okubo,
J. Izumi, T. Hosotani, T. Yamashita, Colloid Polym. Sci. 1997, 275, 797.
[11] a) C. J. McDonald, K. J. Bouch, A. B. Chaput, C. J. Stevens, Macromolecules 2000, 33, 1593. b) J. Jang, K. Lee, Chem. Commun. 2002, 1098.
[12] a) K. Kalyanasundaram, J. K. Thomas, J. Am. Chem. Soc. 1977, 99, 2039.
b) C. Honda, M. Itagaki, R. Takeda, K. Endo, Langmuir 2002, 18, 1999.
[13] F. M. Winnik, Chem. Rev. 1993, 93, 587.
[14] M. Pope, C. E. Swenberg, Electronic Processes in Organic Crystals and
Polymers, 2nd ed., Oxford University Press, Oxford 1999, Ch. 1.
[15] S. Keuker-Baumann, H. Bock, F. D. Sala, S. A. Benning, T. Haheider,
T. Frauenheim, H. S. Kitzerow, Liq. Cryst. 2001, 28, 1105.
[16] a) Y. Yang, A. J. Heeger, Appl. Phys. Lett. 1994, 64, 1245. b) J. Gao, A. J.
Heeger, J. Y. Lee, C. Y. Kim, Synth. Met. 1996, 82, 221.

Multifunctional Sodium Lanthanide Silicates:

From Blue Emitters and Infrared S-Band
Amplifiers to X-Ray Phosphors**
By Duarte Ananias, Artur Ferreira, Lus D. Carlos,* and
Joo Rocha*
Luminescence materials, or phosphors, are found in a wide
range of everyday applications, such as cathode ray tubes, projection televisions, infrared amplifiers, and X-ray detectors.[1]
Display and lighting technology is pushing for more rugged,
and power-efficient, and smaller systems.[2] It is believe that
these needs will be met best through use of individually colored light-emitting devices (LEDs). However, the mixing of
red, green, and blue LEDs in a single system raises difficulties
in integration of the individual LED materials and electrical
requirements.[2,3] Thus, in general, it is crucial to combine
different optical functionalities in a single material (GaN, for
instance),[2] or, alternatively, in a chemically compatible multilayer sandwich device.
Here, we report a step forward towards this goal: the synthesis of isomorphous sodium lanthanide silicate materials,
Na3(Y1aMa)Si3O9 (M = Tm3+, Tb3+; a = 01). In this system,

[*] Prof. J. Rocha, Dr. D. Ananias

Department of Chemistry, University of Aveiro, CICECO
P-3810-193 Aveiro (Portugal)
E-mail: rocha@dq.ua.pt
Prof. A. Ferreira
ESTGA, University of Aveiro, CICECO
P- 3810-193 Aveiro (Portugal)
Prof. L. D. Carlos
Department of Physics, University of Aveiro, CICECO
P-3810-193 Aveiro (Portugal)
E-mail: lcarlos@fis.ua.pt

[**] The Financial support from FCT, POCTI, and FEDER is gratefully acknowledged. We thank J. Soares and M. Soares for assistance in luminescence and X-ray measurements.

DOI: 10.1002/adma.200304474

Adv. Mater. 2003, 15, No. 12, June 17

Adv. Mater. 2003, 15, No. 12, June 17

http://www.advmat.de

radiation diagnostic imaging systems. Gd2O2S:Tb is one of the

most efficient X-ray phosphors used in imaging detectors and
intensifying screens, both for high voltage applications (such
as abdominal imaging, chest radiography, lumbar spine radiography, and computer tomography), and very low-voltage
applications (e.g., mammography).[2326]
Na3(Y1aMa)Si3O9 materials studied here possess the mixed
(M) octahedral(Si) tetrahedral framework exhibited by
Na3YSi3O9. The main features of this rather complicated crystal structure are illustrated in Figure 1.[27] Na3YSi3O9 has been
the subject of several ionic conductivity studies,[28,29] and,
when doped with Eu3+, photoluminescence characterization.[30] Moreover, Na3ErSi3O9 is a C-band infrared emitter.[31]

Fig. 1. Main features of the structure of the Na3MSi3O9 (xy0 projection) [29].
The MO6 octahedra are isolated from one another, while the corner sharing SiO4
tetrahedra form an unusual type of siliconoxygen radical, infinite in one dimension-spiral: a spiral meta-chain (Si12O36) (with period b = 15.14 ) with alternate links of twelve SiO4 tetrahedra. Since these twelve tetrahedra constitute
only a half-wave, the complete wave consists of 24 tetrahedra and, thus, the formula of the chain is (Si24O72). In the links of this chain there are triortho groups
(Si3O10). The terminal oxygen atoms of the adjacent triortho groups along [001]
are merged yielding a new type of meta chain. There are four such chains in the
unit cell. The free vertices of the chains rest on MO6 octahedra. In the cavities of
the mixed octahedral-tetrahedral framework there are Na+ cations.

Na3(Y1aTma)Si3O9 materials exhibit blue emission with

excellent color purity, the most efficient member of the series
being Na3(Y0.98Tm0.02)Si3O9 (Fig. 2). The emission spectra of
this phosphor, measured at 14 and 300 K, are shown in Figure 3. The emission lines are assigned to the prominent
1
D2 3F4 and to 1G4 3H6 transitions, while the excitation
line is due to the 3H6 1D2 transition (inset Fig. 3). Raising
the temperature from 14 to 300 K broadens all spectral lines
and their integrated intensity decreases. For example, the integrated intensity of the 1D2 3F4 emission (excited at
357.5 nm) decreases ca. 36 % (not shown) at 300 K. Due to
the temperature activation of the excited levels of the 1D2 singlet, the excitation lines shift to the red (from ca. 357.5 to
360 nm). No sample emission degradation under continuous
irradiation was observed. The chromaticity (x,y) CIE coordinates, the dominant wavelength, and color purity (Fig. 4) were

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the thulium-based materials display quite unusual room-temperature (RT) luminescence features in the blue and infrared
regions. The mixed thuliumyttrium members of the series,
Na3(Y1aTma)Si3O9, exhibit a blue emission with (x,y) CIE
(Commission Internationale de L'Eclairage) color coordinates and color purity comparable to, or better than, those reported for the most-used blue phosphors.[1,46] The sthoichiometric thulium silicate, Na3TmSi3O9, in turn, shows a broad
RT infrared emission within the E- (extended, 1360
1460 nm), S- (short, 14601530 nm), and C- (conventional,
15301565 nm) bands, essential for the new generation of silica-based thulium-doped fiber amplifiers.[710] Doping this
material with yttrium, and controlling the Y3+/Tm3+ molar
ratio, allows fine-tuning of the infrared emission between the
S- and the O- (original, 12601360 nm) bands. Moreover, terbium-based sodium silicates, Na3(Y1aTba)Si3O9, are new and
highly efficient X-ray phosphors with potential applications in
medical diagnostic imaging systems (ca. 25 % brighter than
standard Gd2O2S:Tb).
Thulium-doped materials have attracted much interest in
the last few years because they are efficient blue phosphors
with potential applications in screens and displays, such as
cathode-ray tubes, vacuum fluorescent and field-emission displays, and electroluminescent devices.[1,11,12] The use of Tm3+based materials as sources of blue coherent radiation is another emerging field.[1316] Indeed, oxides such as Y2O3:Tm3+,
Y2Al5O12:Tm3+, and SrHfO3/Tm3+ are viable alternatives to
the presently used metal sulfides (ZnS:Ag and
ZnS:Tm,F).[4,11,17,18] Although the latter are the most efficient
blue emitters available, they have important drawbacks, such
as luminance saturation at high excitation density,[17] emission
degradation during operation,[4] and corrosion of the emitter
cathodes in field-emission displays induced by sulfur-related
contaminant gases.[11]
Thulium-based materials are also finding applications in the
field of fiber optics. The increase in optical communications
traffic is stimulating much research into the development of
highly efficient broadband fiber amplifiers for wavelength division multiplexing network systems.[7,8,19,20] Silica-based
transmission fibers have a wide window from 1400 to 1700 nm
and, thus, there is an emerging demand for optical amplifiers
usable in this range. However, the presently available erbiumdoped fiber amplifiers for dual-wavelength-band only operate
within the C-[20] and L- (long, 15651625 nm) bands.[21] The
next step is to use the S-band, taking full advantage of the
14601530 nm low-loss window of optical fibers. Thuliumdoped fiber amplifiers operating at 14751510 nm, in a configuration similar to the existing erbium-doped fiber amplifiers,
have been recently reported.[710]
Terbium-doped materials have been used as X- or c-radiation-to-light converters in medical diagnostic imaging detectors, reducing the exposure of the patient to X-rays while preserving the quality of the X-ray image.[22] Phosphor
intensifying screens absorb and convert X-ray photons into
visible or UV light, which is recorded by optical detectors
(films, photocathodes, or photodiodes), incorporated in the

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Fig. 2. Na3(Ya1Tma)Si3O9 1D2 3F4 transition, excited at 360 nm and recorded
at RT.

Fig. 4. CIE chromaticity diagram showing the RT (x,y) color coordinates for
Na3(Y0.98Tm0.02)Si3O9 (excitation wavelength 360 nm) and standard blue emitters Y2O3:Tm, Sr2B5O9Cl:Tm, BaMgAl10O17:Eu, and ZnS:Ag.

Fig. 3. Visible emission spectra of Na3(Y0.98Tm0.02)Si3O9 excited at 357.5 nm

and recorded at 14 (solid line) and 300 K (dotted line). The inset shows the
excitation spectra detected within the 3F4 manifold (448.5 nm).

determined from the emission spectrum of Na3(Y0.98Tm0.02)Si3O9. The values obtained, (0.147,0.029), ca. 458 nm and
99 %, respectively, are superior (particularly the very high
color purity) to the values reported for standard blue phosphors, such as Y2O3:Tm, (0.158,0.150),[4] Sr2B5O9Cl:Tm
(0.166,0.115),[5]
BaMgAl10O17:Eu
(0.147,0.067),[6]
and
[1]
ZnS:Ag, (0.145,0.081) (also shown in Fig. 4).

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2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The efficiency of the blue 1D2 3F4 RT emission may be

tuned by adjusting the Y3+/Tm3+ molar ratio, as illustrated in
Figure 2. To allow a qualitative comparison, the spectra were
recorded consecutively by keeping the experimental set-up
fixed (slits width, irradiated area, optics geometry). The powders were pelleted to approximately the same pressure
( 107 kg m2) to insure that multiple scattering between
grains does not affect the effective optical path and, thus, the
absorption cross-section.
Lifetime measurements of the 1D2 emitting level were carried out at RT, with 355 nm excitation, on the sample with the
lowest Tm3+ content, Na3(Y0.98Tm0.02)Si3O9, in order to minimize effects of interactions between optically active ions. The
curve obtained (not shown) is clearly bi-exponential, with
fitted lifetimes of 64 12 and 144 24 ls. These values and the
values previously reported for other thulium-based materials,
such as LaF3:Tm3+[32] and Ca4Gd1aTmaO(BO3)3,[33] are of the
same order of magnitude. The presence in our samples of four
optically active Tm3+ local sites[27] may explain the bi-exponential nature of the 1D2 decay curve for samples with low activator concentrations [0.13 at.-% for Na3(Y0.98Tm0.02)Si3O9],
where direct donoracceptor relaxation between Tm3+ ions is
negligible.[11,32,33] The fact that only two of the four expected
lifetimes are detected suggests that some of the values may be
very similar and, hence, undistinguishable with the experimental set-up used. In Na3YSi3O9, three Y3+ local sites have very
similar first-coordination-shell radii (2.2482.253 ) while the
fourth site coordination shell is slightly larger (2.273 ). Since
Na3(Y1aTma)Si3O9 and Na3YSi3O9 samples are isostructural,

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Adv. Mater. 2003, 15, No. 12, June 17

ing of the infrared emission may be easily achieved by controlling the samples Y3+ content.
In addition, because the 3H4 3H6 lines at ca. 800 nm display a very low relative intensity, the preferential 3H4 level radiative-decay channel in these materials is the 3H4 3F4 transition. According to the JuddOfelt theory, this is a totally
unexpected result because the 3H4 3H6 transition branching
ratio is about eleven times the typical value for the 3H4 3F4
lines.[8] The suppression of the 3H4 3H6 spontaneous emission is essential to avoid lasing at unexpected wavelengths because it results in the improvement of the amplifier performance within the S-band. In thulium-doped fiber amplifiers
presently used this suppression is normally achieved by promoting the inversion of population using an up-conversion
pumping scheme or, alternatively, by quenching the 3F4 and
3
H4 levels through energy transfer with Ho3+ and Nd3+.[8]
The incorporation of terbium into our sodium silicate system results in efficient X-ray phosphors. The X-ray-excited
spectra of Na3(Y0.74Tb0.26)Si3O9 and reference X-ray phosphor Gd2O2S:Tb (Fig. 6) display typical 5D4 7F63 Tb3+
transitions. The integrated intensity (inset Fig. 6) of samples
with a = 0.26 (solid line) and 0.48 (dotted line) is larger than
that of the standard phosphor. For the former (best sample)
the integrated intensity is ca. 27 % higher than that of
Gd2O2S:Tb. The photographs inset in Figure 6 demonstrate
this visually.
The work reported here opens new research avenues for
the integration of different optical functionalities in a single

Fig. 5. Infrared emission spectra of Na3TmSi3O9 (solid line) and Na3(Y0.98Tm0.02)Si3O9 (dotted line) excited at
476.5 nm and recorded at 75 and 300 K. The inset displays the variation with the Tm3+ content of the ratio between
the 75 K integrated intensities of the E-, S-, C- (3H4 3F4, 3F2 3H5), and O- (1G4 3H4, 3H5 3H6) bands.

Adv. Mater. 2003, 15, No. 12, June 17

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we ascribe the shorter lifetime to the Tm3+ local site with the
longest first coordination shell radius (longest average Tm3+O
bond). Since all four sites are hexa-coordinated, a long Tm3+
O bond corresponds to a less covalent and less rigid local environment.[34,35] Thus, the three local sites with very similar average radii may have almost identical (and longer) lifetimes.
Samples with higher Tm3+ content display a clearly non-exponential faster decay, due to concentration-quenching effects
occurring via cross-relaxation between ions.[11,32,33]
The thulium-based materials reported here display broad
RT infrared emission in the range 1360 to 1565 nm. For example, the spectrum of Na3TmSi3O9 consists of two series of
lines, within the E-, S-, and C-bands, assigned to the 3H4 3F4
(maximum at ca. 1430 nm) and 3F2 3H5 (maximum at ca.
1530 nm) transitions, respectively (Fig. 5). Raising the temperature from 75 to 300 K broadens the Stark components
and decreases, by ca. 62 %, the integrated intensity of these
two transitions (not shown). The relative intensity of the
3
H4 3F4 and 3F2 3H5 transitions decreases with decreasing
Tm3+ content, and the 1G4 3H4 and 3H5 3H6 lines within
the O-band dominate the infrared emission (Fig. 5). Clearly,
as the isomorphic substitution of Y3+ by Tm3+ increases, a
larger number of Tm3+ ions undergo 3H4 3F4 and 3F2 3H5
transitions, whereas the simultaneous 1G4 3H4 and
3
H5 3H6 infrared emission is suppressed. The ratio between
the integrated intensity of the emissions within the E-, S-, and
C-bands and the emissions within the O-band increases linearly with increasing Tm3+ content (inset Fig. 5). Hence, fine-tun-

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Fig. 6. X-ray-excited visible luminescence spectra (and photographs, emitting
spot ca. 1 cm2) of Na3(Y0.74Tb0.26)Si3O9 (solid line, photograph A) and standard
Gd2O2S:Tb phosphor (dotted line, photograph B). The sharp lines are assigned
to the Tb3+ 5D4 7F63 transitions. Spectra were recorded using the same
experimental conditions. The slits width of the X-ray monochromator and the
irradiated area were fixed and both the position of the samples and the orientation of the high sensitivity fiber optic were exactly the same in all measurements. The inset shows the Na3(Y1aTba)Si3O9 luminescence integrated intensity normalized to the intensity of Gd2O2S:Tb . The line is a guide for the eyes.

material. Although the materials studied contain only yttrium

and a second rare-earth metal, preliminary work shows that it
is possible to obtain Na3(Y,Eu,Tb,Tm)Si3O9 samples via hydrothermal synthesis. Each sample is a full-colour phosphor
displaying visible (bluegreenred) and infrared (S-band)
emission and X-ray-induced luminescence. The next step is to
prepare films of these full-color phosphors. Alternatively,
because the different sodium (yttrium, lanthanide) silicate
materials are isostructural, it may be possible to prepare and
process multilayer films.
In conclusion, the synthesis and optical properties of lanthanide silicates in the system Na3(Y1aMa)Si3O9 (M = Tm3+,
Tb3+; a = 01) have been studied. It has been shown that a judicious choice of the lanthanide cation and its content in the
materials allows a remarkably wide-range tuning of the optical properties. The materials obtained, all possessing the same
basic framework structure, encompass very efficient terbiumbased X-ray phosphors, with real potential for applications in
medical diagnostic imaging, and thulium-based materials displaying: i) broad RT infrared emission (ca. 13601565 nm), essential for the new generation of silica-based thulium-doped
fiber amplifiers; and ii) blue emission with excellent color purity. Moreover, the tuning of the infrared emission between the
S- and the O-bands is easily achieved by controlling the Y3+/
Tm3+ molar ratio. This unusual sodium lanthanide silicate system is, thus, highly tunable and multifunctional.

Experimental
Materials: In a typical Na3TmSi3O9 synthesis an alkaline solution was made by
mixing 2.99 g sodium silicate solution (27 wt.-% SiO2, 8 wt.-% Na2O, Merck),
15.21 g H2O, 2.66 g NaOH (Merck). An amount of 0.53 g of TmCl36H2O (Aldrich) was added to this solution, and the mixture was stirred thoroughly. The

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2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

gel, with composition Na2O/SiO2/Tm2O3/H2O 2.76:1.00:0.051:70.8, was reacted

in Teflon-line autoclaves (volume 45 cm3, filling 35 %), under static conditions
and autogenous pressure for 7 days at 230 C. The autoclaves were then removed
and quenched in cold water. The microcrystalline white powder was filtered,
washed at RT with distilled water, and dried at 100 C. Na3(Y1aTma)Si3O9
(a = 0.020.2) samples were synthesized by introducing the desired Tm3+ and Y3+
(starting reagent YCl36H2O, Aldrich) contents in the initial gel. Na3(Y1aTba)Si3O9 (a = 0.11.0) samples were prepared in a similar way but using Y3+ and Tb3+
(starting reagent TbCl36H2O, Aldrich).
Inductively coupled plasma analysis was performed by Kingston Analytical
Services, UK. Powder X-ray diffraction data were collected on a X'Pert MPD
Philips diffractometer (Cu Ka Xradiation) with a curved graphite monochromator, a fixed divergence slit of 0.25, and a flat-plate sample holder, in a
BraggBrentano para-focusing optics configuration. Intensity data were collected by the step-counting method (step 0.03 and time 10 s) in the range 2h
12140. Rietveld refinements were carried out with Fullprof [36] using the
atomic coordinates given by Maksimov et al. [27] and space group P212121
(n = 19). As examples, for samples Na3TmSi3O9 and Na3(Y0.96Tm0.04)Si3O9
(brackets) the following cell parameters were obtained, respectively: a = 15.163
(15.203), b = 15.089 (15.137), c = 15.004 (15.043) .
Visible spectra (14300 K) were recorded on a Jobin YvonSpex spectrometer (HR 460) fitted with a 1200 grooves mm1 grating blazed at 500 nm, coupled
to a R928 Hamamatsu photomultiplier. A 150 W Xe arc lamp coupled to a excitation monochromator Jobin YvonSpex (TRIAX 180) fitted with a 1200
grooves mm1 grating blazed at 330 nm was used as excitation sources. Infrared
emission spectra (75300 K) have been obtained on a Bruker IFS 66v Fourier
transform infrared (FTIR) spectrometer coupled to a Ge North-Coast EO-817
photodiode cooled to 77 K. The 476.5 nm line of an Ar ion laser was used as
the excitation source. All the spectra were corrected for the response of the detectors. Time-resolved Tm3+ spectra (visible region) were recorded using the
third harmonic generation of a pulsed Continuum Serulite SL II 10 Nd:YAG
laser (pulse of 57 ns). The detection system is an ANDOR ICCDs. The X-ray
induced PL was recorded with a plug-in high sensitivity fiber optic UV-vis
shortwave master spectrometer, fitted with a 600 grooves mm1 grating blazed
at 500 nm, with a 2048-element linear CCD-array detector (PC 2000, Ocean
Optics, Inc.). The PC 2000 was mounted on a 1 MHz ISA-bus A/D card installed directly into a desktop PC. The X-ray beam of a X'Pert MPD Philips diffractometer (Cu Ka radiation, 8.050 keV, 40 kV) was used as the incident excitation source.

Received: September 30, 2002

Final version: March 14, 2003

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http://www.advmat.de

Adv. Mater. 2003, 15, No. 12, June 17

Patterned Alignment of Liquid Crystals

on Selectively Thiol-Functionalized
Photo-Orientation Layers**
By Hans T. A. Wilderbeek,* Jean-Pierre Teunissen,
Cees W. M. Bastiaansen,* and Dirk J. Broer*
Electro-optical devices are key in current information and
communication technology. Whereas the familiar cathode ray
tube can be considered to be a mature technology, other
device principles, such as plasma-addressed devices,[1] and
field-emission,[2] electroluminescent,[3,4] electrochromic,[5] and
electrophoretic displays,[6] are still at various stages of development, implementation, and market acceptance. Flat and
light-weight liquid-crystal-based devices are currently considered to be the main alternative to the cathode ray tube, and
various switching principles have been developed, such as
p-cells,[7] twisted[8] and super-twisted nematic,[9] ferroelectric,[10] and vertically aligned nematic[11] liquid-crystal displays. Devices based on these different principles all have
their own specific advantages with respect to characteristics
such as switching kinetics, switching voltages, energy consumption, and viewing angle dependency. In order for these
devices to function optimally, microscopic control over the
director of the liquid-crystal molecules within the device is
required. This is enforced by the boundary conditions of the
liquid-crystal layer, and is preferably realized through alignment layers. Whereas conventional uniaxial alignment is sufficient for less demanding applications, more sophisticated, patterned alignment is needed to improve the optical

[*] Dr. H. T. A. Wilderbeek, Prof. D. J. Broer

Philips Research Laboratories
Professor Holstlaan 4, NL-5656 AA Eindhoven (The Netherlands)
E-mail: hans.wilderbeek@philips.com; dick.broer@philips.com
Dr. C. W. M. Bastiaansen, J. P. Teunissen
Dutch Polymer Institute, Eindhoven University of Technology
P.O. Box 902, NL-5600 AX Eindhoven (The Netherlands)
E-mail: c.w.m.bastiaansen@tue.nl

[**] The authors acknowledge Otto van Asselen for his contribution to the IR
measurements. The Dutch Polymer Institute is also gratefully acknowledged for its funding of this project.

Adv. Mater. 2003, 15, No. 12, June 17

DOI: 10.1002/adma.200304759

performance of devices further, for instance with respect to

the viewing angle. One application of patterned alignment is
in multidomain displays that exhibit reduced viewing angle
dependence and reduced gray-scale inversion.[12,13]
Several methods can be used to align liquid crystals. Traditionally, surfactants or mechanical rubbing methods of polyimides are employed.[14] However, this procedure requires
direct mechanical contact, which introduces defects and is a
source of electrostatic discharge and dust. The patterned
alignment in different directions on a single substrate requires
the additional use of photoresists, which is both laborious and
cumbersome. Photo-alignment using (linearly polarized) light
in combination with a photomask offers a non-contact alternative that enables bi-directional control over the alignment.[1517] However, accurate and reproducible control over
the pretilt angle of the liquid crystals is complicated, and the
technique suffers from adverse side effects such as image
sticking. It is also extremely difficult to realize control over
both the azimuthal and polar anchoring of the liquid crystals
within a single substrate. Combinations of both unidirectional
planar (in the plane of the substrate) and homeotropic (perpendicular to the plane of the substrate) alignment of liquid
crystals within a single substrate has been realized using micro-contact printing of self-assembled monolayers on relatively thick, semi-transparent gold layers,[18] and on transparent
ultra-thin gold layers.[19] Other reported alignment methods,
such as the use of expensive atomic beams, also only provide
bi-directional control of the azimuthal anchoring and have no
or only limited control over the polar anchoring angle.[20]
In this paper, we describe a novel method that enables full
control over the azimuthal and polar anchoring directions by
using selectively deposited thiols that are covalently linked to
photoalignment layers. This provides a simple and versatile
way of combining both bi-directionally planar and homeotropic alignment of liquid crystals within a single substrate. Thin
layers of common, uncured linearly photopolarizable (LPP)
derivatives were spun on glass substrates covered with a transparent layer of indium tin oxide. The final photoalignment
layers are conventionally produced using E/Z isomerism,
photodegradation or 2+2 cycloaddition, as is particularly observed for cinnamate and coumarin derivatives.[21] Here, the
unsaturations present in the polarizable groups of commercially available cinnamate or coumarin LPP derivatives were
functionalized to induce a different alignment of liquid crystals. We used the familiar free-radical thiolene addition reaction to do this (Scheme 1),[22] inspired by the successful use of
thiols in self-assembled monolayers to induce various alignments of liquid crystals.[18,19] The unexposed or locally unexposed LPP material was therefore covered with a thiol (e.g.,
n-dodecanethiol) containing a small amount of a thermal initiator. The addition of the thiol group to the unsaturations
present in the LPP material was initiated thermally, by subjecting the substrates to an elevated temperature (e.g., 130 C)
but still sufficiently low to avoid thermal initiation of the competitive 2+2 cycloaddition reaction of the uncured LPP films.
We chose to use a thermal initiator, although in principle ad-

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

985

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