FULL PAPER

DOI: 10.1002/adfm.200601117

Large-Size Bulk and Thin-Film Stilbazolium-Salt Single Crystals

for Nonlinear Optics and THz Generation**
By Zhou Yang,* Lukas Mutter, Marcel Stillhart, Blanca Ruiz, Shanmugam Aravazhi, Mojca Jazbinsek,
Arno Schneider, Volker Gramlich, and Peter Günter

We present new stilbazolium salt DSTMS (4-N,N-dimethylamino-4′-N′-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate)

with both high second-order nonlinear optical properties and very favorable crystal growth characteristics. We are able to ob-
tain very large area bulk single crystals of more than 3 × 3 × 0.2 cm3 with a high optical quality without using seed crystals by
using low-temperature solution growth. We also demonstrate the growth of single crystalline thin films of DSTMS with an area
of up to 6 × 5 mm2 and a thickness between 5–30 lm. Nonlinear optical measurements reveal that DSTMS possesses large non-
linear optical susceptibilities with v111(2) = (430 ± 40) pm V–1 at 1.9 lm. Highly efficient generation of broadband THz waves
with THz electric field strengths of more than 4 kV cm–1 using 160 fs laser pump pulses at a wavelength k = 1.45 lm and
DSTMS crystals has been demonstrated.

1. Introduction positively charged nonlinear optical chromophore stilbazolium

and a negatively charged tosylate anion. The counter-ion tosy-
During the last two decades, there have been intensive re- late is used in order to override the preferred antiparallel crys-
search efforts in exploring and developing second-order non- tallization of the chromophores. Up to date, DAST is the only
linear optical (NLO) materials for applications such as fre- commercially available organic nonlinear optical crystal.[12]
quency conversion, electro-optic modulation and optical However, its growth is still a challenge and there are many
parametric oscillation,[1–4] and more recently, THz generation groups investigating the growth of bulk and thin films of
and detection.[5] Compared with inorganic materials, molecular DAST.[13–16] For example, one of the challenges is to reduce the
organic materials have been of considerable interest due to growth time needed to obtain high optical quality DAST, which
their large nonlinear optical properties, ultrafast response takes several weeks for crystals with dimensions exceeding
times and almost unlimited design possibilities.[6,7] Among 1 cm3.[12]
them, organic crystals based on the charged chromophores and Although DAST shows large electro-optic effects, the devel-
strong Coulomb interaction have several advantages over non- opment of new organic crystals with larger electro-optic coeffi-
ionic species, such as large molecular nonlinearity or first-order cients and (or) faster and easier crystal growth procedure is an
hyperpolarizability (b), long-term stability and a higher ten- important challenge for future applications. It has already been
dency to override the dipole-dipole interactions and thus form demonstrated that varying the counter-ion to optimize the crys-
non-centrosymmetric macroscopic packing.[8,9] For example, tal packing and orient the dipoles as parallel as possible is an
the organic salt crystal, 4-N,N-dimethylamino-4′-N′-methyl-stil- effective molecular engineering strategy to develop ionic or-
bazolium tosylate (DAST) is one of the best nonlinear optical ganic crystals with non-centrosymmetric structure.[17–20] Using
materials with large second-order nonlinear optical susceptibil- this approach, we have reported the synthesis and crystal
ities v111(2) = (2020 ± 200) pm V–1 at 1.3 lm and growth of DSNS (4-N,N-dimethylamino-4′-N′-methyl-stilbazo-
v111 = (420 ± 110) pm V–1 at 1.9 lm due to the good alignment
(2) lium 2-naphthalenesulfonate)—a promising DAST derivative
of the chromophores in the crystal.[10,11] DAST consists of a with perfectly aligned chromophores, leading to a 50 % higher
nonlinearity in the crystalline powder than DAST.[21] However,
only very small crystalline needles of DSNS with a diameter of
less than 100 lm could be grown.[21] We are therefore looking
– for a new highly nonlinear compound that could easily give
[*] Dr. Z. Yang, L. Mutter, M. Stillhart, B. Ruiz, Dr. S. Aravazhi, crystals of large area suitable for bulk and thin film applica-
Dr. M. Jazbinsek, Dr. A. Schneider, Prof. P. Günter
Nonlinear Optics Laboratory, Institute of Quantum Electronics tions. We present here a new promising DAST derivative (see
ETH Zurich, 8093 (Switzerland) Scheme 1) with high solubility that is more than two times the
E-mail: nlo@phys.ethz.ch one of DAST in methanol at the same temperature. We show
Prof. V. Gramlich that organic crystals with similar nonlinear optical properties
Laboratory of Crystallography, Department of Materials
ETH Zurich, 8093 (Switzerland) as DAST are feasible with a considerably faster crystal growth
[**] This work has been supported by the Swiss National Science Founda- rate and much better perspectives for growing single crystalline
tion. thin films for integrated optics.

2018 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2007, 17, 2018–2023
Z. Yang et al./Stilbazolium-Salt Single Crystals

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The temperature dependence of the solubility of a dilute so-
N
N CH3 lution, considering that the solute dissolves into two ions, can
be described by[22]

SO3
   
DS DH
xs ˆ exp exp 1†
2R 2RT
Scheme 1. Molecular structure of DSTMS.
where xs is the molar fraction of the solute at saturation,
R = 8.314 J mol–1 K–1 is the gas constant, and T the temperature
in K. The thermodynamic parameters DS and DH are the
2. Results and Discussion changes of the entropy and enthalpy when dissolving the sol-
ute. The measured solubility S (in g of solute per 100 g of sol-
2.1. Synthesis and Characterization
vent) is related to the molar fraction of the solute xs as
4-N,N-dimethylamino-4′-N′-methyl-stilbazolium 2,4,6-tri- S = 100 (Msolute/Msolvent) xs/(1 – xs), where Msolute/solvent is the
methylbenzenesulfonate (DSTMS) was synthesized according molecular mass of the solute/solvent. Analyzing the solubility
to the procedure described previously.[18] The product was puri- data using Equation 1 shows that both DS and DH are larger
fied by recrystallization (three times) from methanol before for DSTMS compared to DAST and can be considered con-
characterization by NMR and elemental analysis. It was easy stant in the temperature region of interest (see Fig. 1).
to obtain orange color hydrate centrosymmetric crystals in the An important parameter that affects the growth rate in solu-
presence of water and the water could be removed by heating tion-growth systems is the driving force for crystallization
above 100 °C for 1–2 h. Dl = ls – lc, defined by the difference between the chemical po-
DSC and TGA analyses have shown that the melting point tential of the solute in the solution ls and in the crystalline
of DSTMS is (258 ± 1) °C and begins to decompose at around phase lc. If we increase the concentration of the solute in the
250 °C. solution from xs to xs′, the driving force can be expressed sim-
DSTMS can be well dissolved in some strong polar solvents ply as Dl = 2RT (lnxs′ – lnxs)[22] or with the level of supersatura-
such as methanol, DMF and DMSO etc.. However, DMF and tion r = (xs′ – xs)/xs as Dl = 2RT ln(1 + r) ≈ 2RT r. Supersatura-
DMSO are not well suited for crystal growth because of their tion in our system is achieved by lowering the temperature of
high boiling points. Therefore methanol was chosen as the sol- the saturated solution from T′ to T. Using Equation 1 and con-
vent for the growth of DSTMS crystals. Figure 1 shows the sol- sidering small DT = T′ – T we obtain for the driving force
ubility curve for DSTMS in methanol solution in comparison Dl = (DT/T) DH. Therefore, an increased driving force for crys-
with DAST. The solubility at a temperature T was measured by tallization of DSTMS compared to DAST is expected due to
saturating the solution at a higher temperature (about 5 °C larger DH when lowering the temperature of the saturated so-
above T), slowly cooling it in the presence of a precipitated sol- lution by DT.
id to maintain equilibrium, and then analyzing the solution at
the temperature T. The solubility of DSTMS is around two 2.2. Crystal Growth and X-Ray Crystallographic Study
times as large as the one found in DAST in methanol at the
same temperature in the temperature range of interest. The It was found that DSTMS nucleated very easy and fast.
large difference in the solubility can mainly be attributed to From the recrystallization procedure to purify the material
the different structure of counter-anions—the solubility of we were already able to get optical quality thin single-crys-
2,4,6-trimethyl-benzenesulfonate that possesses three methyl talline plates with dimensions of 5 × 5 × 0.3 mm3. Contrary to
groups should be higher than that of tosylate that possesses DAST, we are able to easily grow large bulk DSTMS crystals
only one methyl group. without a seed given the improved growth characteristics of
the latter. Slow cooling technique was adapted for the
growth of bulk crystals.[20] First we prepared saturated solu-
tion of DSTMS in methanol at 35–40 °C. Spontaneous nucle-
Solubility (g/100g solvent)

20
DSTMS ation could be observed after cooling down the saturated so-
15
DAST lution. Then we increased the temperature to dissolve most
10 of the nuclei and made sure that only one or two nucleated
crystals remained undissolved. After that, large crystals with
5 very good optical quality for optical measurements could
be grown by slow cooling the solution at a rate of
0
20 30 40 50 60 0.2–0.3 °C day–1. Typically the crystals first appear as red thin
Temperature (ºC) plates and continue to grow preferentially along the edges in
all directions. DAST, on the other hand, prefers to grow only
Figure 1. Solubility/temperature curves of DSTMS and DAST in methanol.
The solid curves are according to equation (1) with DH = (81 ± 4) kJ mol–1
along the direction of the polar axis [–100].[16] Using this
and DS = (170 ± 10) J mol–1 K–1) for DSTMS and DH = (74 ± 3) kJ mol–1 and self-nucleating method we can eliminate the defects intro-
DS = (140 ± 10) J mol–1 K–1 for DAST. duced by seeds and omit the process of selecting, processing

Adv. Funct. Mater. 2007, 17, 2018–2023 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.afm-journal.de 2019
 Z. Yang et al./Stilbazolium-Salt Single Crystals
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and fixing the seed crystals. Large single crystal with dimen- Table 1. Crystallographic and other data of DSTMS and DAST crystals. hlz
sions of 33 × 33 × 2 mm3 have been grown by this method in a is the angle between the long axis of the cation chromophores and the po-
lar axis of the crystal, Tm the melting temperature and v111(2) the element
period of eight weeks (Fig. 2a). Experiments show that we of the second-order nonlinear optical susceptibility tensor for second-har-
can grow high quality single crystals of DSTMS with surface monic generation at fundamental wavelength of 1.9 lm.

Sample DSTMS DAST

Formula C25H30N2O3S C23H26N2O3S

FW 438.57 410.52
Crystal system Monoclinic Monoclinic
Space group Cc Cc
a(Å) 10.266 10.365
b(Å) 12.279 11.322
c(Å) 17.963 17.892
a(°) 90 90
b(°) 93.04 92.24
c(°) 90 90
V(Å3) 2261.2 2099.7
hz(°) 23 20
Tm(°C) 258 ± 1 256 ± 1
v111(2) (pm/V) 430 ± 40 420 ± 110

a)
Figure 2. a) DSTMS bulk crystal (size 33 × 33 × 2 mm3), the large surface
is the (001) face. b) DSTMS thin film crystal (size 6 × 5 × 0.03 mm3) grown
by the capillary method.
0,a c
c
area of about 1 cm2 in 2 weeks, thus much faster than that of
DAST (4–6 weeks).
For integrated optics applications the possibility of growing
single crystalline thin films is very attractive. In view of the
good quality of the thin plates spontaneously grown from
DSTMS solution, we have done experiments on thin film
b)
growth by the capillarity method.[16] In this method, two glass
plates are placed together in solution and capillary force pulls
up the liquid. The slow evaporation of the solvent allows for
growth. We have obtained single crystalline thin films with an
area of up to 6 × 5 mm2 and a thickness between 5–30 lm 0,b a
(Fig. 2b).
The crystallographic structure of DSTMS was determined b
via X-ray analysis of single crystals. The data obtained are
listed in Table 1 and compared to the one of DAST. The crystal
packing, which belongs to the monoclinic space group Cc
(point group m, Z = 4), is shown in Figure 3. Crystallographic
c)
data show that beside the Coulombic interactions between the
cation and anion parts, hydrogen bonds between the sulfonic
oxygen atoms and double-bond hydrogen atoms also play a
role in crystal packing and chromophores orientation. Figure 4 0,c a
shows the hydrogen-bonded network formed by two kinds of
Figure 3. Crystal packing of DSTMS projected along the crystallographic
C–H_O hydrogen bonds between the cation layers and the
axes a (a), b (b), and c (c). The mirror symmetry plane is perpendicular to
anion layers with H_O distances of about 2.49 Å and 2.44 Å, the b-axis. The chromophores make an angle of approximately 23° with re-
respectively. spect to the polar a-axis (c).

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Z. Yang et al./Stilbazolium-Salt Single Crystals

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that the sample has good optical surfaces and is free
c from scattering centers within the crystal.

2.4. Nonlinear Optical Properties

2.491 Å The nonlinear optical properties were measured by
the standard Maker Fringe technique.[23] The first
2.437 Å Stokes line at 1907 nm generated in a high pressure
Raman cell filled with H2 and pumped with a Q
switched Nd:YAG at 1064 nm (pulse length of 7 ns)
was used as fundamental wavelength. The generated
2.491 Å second harmonic light at 953.5 nm was detected by a
photomultiplier and referenced to quartz with
b O a v111(2) = 0.554 pm V–1 at 1907 nm.[24] For the measure-
ment of the nonlinear optical susceptibility v111(2) of
Figure 4. Crystal packing diagram of DSTMS projected along the [110] crystallographic DSTMS, polished c plates were used with the dielec-
vector. The molecules are linked by Coulombic interactions between the ionic parts tric x1 axes oriented along the rotation axis of the
and by hydrogen bonds that are indicated by dotted lines.
Maker Fringe experiment. We obtained a value of
v111(2) = (430 ± 40) pm V–1, which is comparable with
the one of DAST v111(2) = (420 ± 110) pm V–1.[24]
2.3. Linear Optical Properties The nonlinear optical properties of DAST and DSTMS can
be also compared by relating microscopic first-order hyperpo-
Light transmission spectra of DSTMS were measured for larizability tensor bxyz with the macroscopic second order non-
light polarized along the polar a-axis, which is most interesting linear optical susceptibility tensor vijk(2).[4] By applying the sim-
for applications, and for light polarized along the crystallo- ple oriented-gas model and considering only the largest optical
graphic b-axis. For this measurement, an as-grown c-plate sam- hyperpolarizability element bzzz for generating second-harmon-
ple with a thickness of 0.77 mm was optically polished. The ic light at frequency 2x we obtain[4]
sample transmission was measured using a Perkin-Elmer
Lambda 9 spectrophotometer along the two main axes and is v111(2)(–2 x,x,x) = N f12x(f1x)2 cos3(h1z) · bzzz(–2x,x,x) (2)
shown in Figure 5. Three absorption bands observed in the in-
frared region at about 1.2, 1.4, and 1.7 lm correspond to over- where N is the number of chromophores per unit volume, f1x,2x
tones of the C–H stretching vibrations and have also been ob- are the local field corrections, and h1z is the angle between the
served in DAST.[11] polar axis 1 in the crystal and the molecular axis z of the chro-
The refractive indices we have measured at the telecommu- mopore. This angle is for DSTMS about h1zDSTMS = 23° (see
nication wavelength of 1.55 lm by an interferometric tech- Fig. 3), which is slightly larger than the reported h1zDAST = 20°
nique.[3] DSTMS crystals are strongly anisotropic with refrac- of DAST. Assuming similar hyperpolarizabilities bzzz in the sol-
tive index of na = 2.07 ± 0.05 along the polar a axis, and id state of DAST and DSTMS due to the same nonlinear opti-
nb = 1.64 ± 0.05 along the b axis. Using the refractive index data, cal active chromophore, similar local field corrections, and tak-
we calculated the optical absorption from the transmission ing into account the change of the angle h1z and the volume of
measurement of Figure 5 by considering Fresnel losses due to the unit cell (see Table 1), we can estimate the ratio
multiple reflections at the crystal surfaces. We determined the v111(2)(DSTMS)/v111(2)(DAST) = 0.9. The measured nonlinear
absorption constants at 1.55 lm as aa = (0.6 ± 0.1) cm–1 and optical susceptibility is however higher, which can be attributed
ab = (0.5 ± 0.1) cm–1 for light polarized along the a-axis and to a decreased influence of the intermolecular interactions that
along the b-axis respectively. Low optical loss measured shows are decreasing the first hyperpolarizability in the solid state of
ionic compounds, due to the larger distance between the chro-
1.0 mophores in DSTMS compared to DAST.
0.8
Transmission

0.6 2.5. THz Generation

0.4 Recently, the science and technology on ultrashort electro-
b-polarized light magnetic pulses with a spectral content in the 0.1 to 10 THz
0.2
a-polarized light
range (THz pulses) have attracted widespread interest and
0.0
0.8 1.0 1.2 1.4 1.6 1.8 2.0 evolved into a useful tool for a number of applications.[25–28]
Wavelength (µm) For example, highly efficient generation and detection of few
Figure 5. Transmission spectra of 0.77 mm thick DSTMS crystal for light
cycle THz pulses using laser pulses at a telecommunication
polarized along the polar a-axis (solid curve) and along the crystal b-axis wavelength of 1.5 lm and DAST crystals has been demonstrat-
(dashed curve). ed.[29] Attracted by the high nonlinear optical properties, THz

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 Z. Yang et al./Stilbazolium-Salt Single Crystals
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generation with DSTMS has been explored by our group. First 4. Experimental
very promising results are shown in Figure 6. We were able to
demonstrate a highly efficient THz wave emission using optical Synthesis. General Considerations: All reagents were purchased as
rectification in a 0.34 mm thick DSTMS crystal with THz elec- high purity (AR grade) from Aldrich and used without further purifica-
tion. Stilbazolium salt was obtained by condensation reaction between
tric field strengths of more than 4 kV cm–1 and a frequency
4-methyl-N-methyl pyridinium iodide, which was prepared from 4-pi-
range of more than 4 THz. As a fundamental optical wave we coline and methyl iodide, and 4-N, N-dimethylamino-benzaldehyde in
used pulses at 1450 nm with a duration of 160 fs and pulse en- the presence of piperidine [18]. The obtained salt was then metathe-
ergy of 30 lJ from an optical parametric generator pumped by sized to 2,4,6-trimethyl-benzenesulfonate by precipitation from water
solution of sodium salt of 2,4,6-trimethylbenzenesulfonic acid. The
an amplified Ti:Sapphire laser. The generated THz wave am-
products were dried in vacuum for 24 h to remove solvents effectively.
plitude was detected using electro-optical sampling with probe 1
H-NMR spectra were recorded on a Brucker 300 MHz spectrometer
pulses at 725 nm with a 0.5 mm thick ZnTe crystal. The effi- on DMSO-d6 solutions. Elemental analyses were performed by the Mi-
ciency of THz generation in DSTMS is comparable to DAST croanalytical Laboratory, ETH. Thermal analysis was conducted on a
under same conditions.[30] A characteristic phonon absorption Perkin-Elmer TGA-7 and DSC-7 spectrometer at a heating rate of
10 °C min–1, respectively.
is observed in both DAST and DSTMS close to 1 THz (see 4-N,N-dimethylamino-4′-N′-methyl-stilbazolium 2,4,6-trimetheylben-
Fig. 6, right). zenesulfonate, DSTMS: Yield 86 %; 1H-NMR (300 MHz, DMSO-d6):
The generated THz amplitude scales with the material figure d = 8.69 (d, 2H, J = 6.6 Hz, C5H4N), 8.04 (d, 2H, J = 6.6 Hz, C5H4N),
of merit v(2)/n2, where v((2) is the second-order nonlinear optical 7.93 (d, 1H, J = 16.2 Hz, CH), 7.60 (d, 2H, J = 8.7 Hz, C6H4), 7.19 (d,
1H, J = 16.2 Hz, CH), 6.80 (d, 2H, J = 8.7 Hz, C6H4), 6.73 (s, 2H,
susceptibility and n the refractive index. Compared to the con- C6H4SO3–), 4.17 (s, 3H, NMe), 3.02 (s, 6H, NMe), 2.49 (s, 6H, 2Me),
ventional inorganic ZnTe crystal, which is widely used to gener- 2.16 (s, 3H, Me). C, H, N analysis calcd. for C25H30N2O3S: C 68.46, H
ate THz waves by optical rectification with v(2)/n2 of about 6.89, N 6.39; found: C 68.42, H 6.85, N 6.36.
15 pm V–1, DSTMS shows an eight times improved figure of X-Ray Crystallography: The crystal structures were measured on
X-ray diffractometers equipped with CCD detectors, solved and re-
merit of about 120 pm V–1. fined with SHELX. For details see the deposited material. CCDC-
277597 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge Crys-
3. Conclusion tallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif
Received: November 21, 2006
In summary, a novel stilbazolium salt DSTMS has been pre- Revised: March 3, 2007
pared from metathesis reaction. With a noncentrosymmetric Published online: August 2, 2007
crystal packing monoclinic space group Cc, DSTMS shows a
much higher solubility in methanol and much better growth –
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