2276 OPTICS LETTERS / Vol. 29, No.

19 / October 1, 2004

Linear and nonlinear optical studies in photonic crystal alloys

Hanifi Tiryaki, Koichi Baba, Przemyslaw P. Markowicz, and Paras N. Prasad
Institute for Lasers, Photonics and Biophotonics, Departments of Chemistry and Physics, University at Buffalo,
The State University of New York, Buffalo, New York 14260

Received April 9, 2004

We report on linear transmittance and ref lectance as well as on third-harmonic generation in photonic crystal
alloys formed by various compositions of polystyrene and poly (methyl methacrylate) colloidal spheres of the
same size. These photonic crystal alloys are structurally ordered but contain refractive-index disorder and
thus provide a random variation of scattering potential. The stopgap shows a monotonic shift in wavelength
as a function of composition that can be fitted by assuming an effective dielectric constant for the colloidal
spheres. In each alloy a dramatic enhancement of third-harmonic generation is observed, always on the
short-wavelength side of the stopgap. © 2004 Optical Society of America
OCIS codes: 190.0190, 160.4670.

Photonic crystals have been a subject of considerable of water. The reaction was initiated by potassium
interest for more than a decade.1 – 3 A great deal of ef- peroxide sulfate (⬃0.2 wt. % against monomer) in an
fort has been put into preparing highly ordered pho- argon atmosphere at 75 ±C and lasted for several hours
tonic crystals for the visible spectral range. Initial to complete polymerization. The size of particles
studies were directed toward the linear optical proper- could be controlled from a few tens of nanometers
ties of these crystals, but more recent studies have fo- to submicrometer by changing concentration of the
cused on nonlinear processes in photonic crystals, and monomer and (or) water temperature. Their sizes
dramatic enhancements of these properties have been were characterized by scanning electronic microscopy
reported.4,5 and found to be ⬃290 nm for PS and ⬃295 nm for
Recently, interest has also been directed toward PMMA. The vertical deposition method of crystal-
studying the effect of disorder in photonic crystals. lization of colloidal crystals, as introduced by Jiang
Part of the motivation has been to investigate et al.,10 was used to prepare colloidal crystal alloys of
electronic analogs of disorder- or defect-induced phe- various volume fraction compositions. These photonic
nomena such as Anderson localization. Another crystal alloys were structurally highly ordered, with
motivation is provided by the use of disorder or defect no difference in shape or size between polystyrene
to create high-quality nanocavities or microcavities and PMMA nanoparticles, as demonstrated by their
and study quantum electrodynamics in these cavities. (scanning electron microscopy) images shown in Fig. 1.
Yet another motivation is provided by the application The refractive indices of PS and PMMA are 1.59 and
of extended defects fabricated in a controlled pathway 1.49, respectively. The thicknesses of the photonic
for optical circuitry. crystal alloys were made to be very close to ⬃11 mm.
In this Letter we report on a type of disorder in Figure 2 shows the ref lectance and the transmit-
photonic crystals in which only a random variation of tance spectra of the photonic crystal alloys for various
refractive index is introduced, without creating any compositions. Impurity-induced defect modes in col-
structural or positional disorder. We refer to such loidal crystals, prepared by using spheres of different
disordered photonic crystals as photonic crystal al- sizes and refractive indices, have been analyzed pre-
loys. The effect of refractive-index disorder in a two- viously.11 In our studies we used spherical particles
dimensional photonic crystal has been theoretically with the same size, and no clear defect states caused
treated by a number of workers.6 – 8 In this Letter by the refractive-index difference between PMMA and
we have used the vertical deposition colloidal crystal PS were noticed, or if they were they could be obscured
method to produce three-dimensional photonic by an average over many types of defect present in
crystal alloys of polystyrene (PS) and poly(methyl the alloy. However, significant widening of the stop
methacrylate) (PMMA) ⬃300-nm spheres in varying band is observed, similar to earlier studies11,12 [see
compositions. The linear optical properties have been Fig. 2(b)]. A gradual monotonic shift in the stopgap
studied by obtaining the ref lectance and transmittance
of these alloys as a function of the volume fraction.
The specific nonlinear optical process studied in these
alloys is third-harmonic generation.
Highly monodispersed PS and PMMA spheres of
⬃300 nm were prepared by using soap-free emulsion
polymerization.9 The polymerization was induced
by using 5.5 ml of styrene monomer solution con- Fig. 1. Scanning electron microscope images indicating a
taining 8 wt. % of divinylbenzene as a cross-linker comparable structural order of photonic crystal alloys of PS
for PS and 5.0 ml of methyl methacrylate solution and PMMA. The ratio of PMMA to PS was (a) 0, (b) 50,
for PMMA. Each solution was poured into 80 ml (c) 100 vol. %. The scale bar in all images is 600 nm.

0146-9592/04/192276-03$15.00/0 © 2004 Optical Society of America

 October 1, 2004 / Vol. 29, No. 19 / OPTICS LETTERS 2277

the bandgap has also been suggested for the trans-

mittance spectra of photonic crystals.7 We have in-
vestigated the long-wavelength side of the bandgap as
a function of composition. Although there appears to
be a slightly enhanced attenuation of transmittance on
the long-wavelength side in the low-composition alloy,
it is not evidence enough to assign it as an Urbach tail.
We plan to develop alloys with a larger scattering po-
tential (refractive-index disorder) to establish the pres-
ence of an Urbach tail.
Recently Markowicz et al.5 reported dramatic
enhancement of third-harmonic generation on the
Fig. 2. (a) Ref lection spectra of photonic crystal alloys. short-wavelength side of the stopgap in a PS colloidal
The PMMA兾PS ratio is 100% (solid curve), 50% (dashed photonic crystal.5 This was attributed to the fulfill-
curve), 0% (dotted curve). (b) Transmission spectra: ment of the phase-matching requirement, because of
100% (solid curve), 50% (dashed curve), 0% (dotted curve).
the anomalous dispersion of the refractive index near
the bandgap. In the present work we have investi-
can be seen. Figure 3 shows a plot of the position gated third-harmonic generation in photonic crystal
of the stopgap as a function of the volume fraction of alloys. For alloys over the entire composition range,
PMMA. an enhancement of third-harmonic generation is ob-
Since the difference between the dielectric constants served, and in all cases it is on the short-wavelength
of PS and PMMA is relatively small, we attempted to side of the stopgap. However, since the position
describe the photonic crystal alloy by treating it as a of the stopgap is dependent on the composition, as
homogeneous photonic crystal made of particles with described above, the wavelength of the maximum
an effective dielectric function given by the equation third-harmonic signal is also compositionally tunable.
This compositional tunability of the third-harmonic
eeff 苷 f1 e2 1 f2 e2 , enhancement confirms a direct relation between the
nonlinear response and the stopgap position, the latter
where e1 , f1 and e2 , f2 are the dielectric constants and being determined by the linear properties of the pho-
volume fractions of the PS and PMMA, respectively. tonic crystal alloys. Figure 4 shows representative
These photonic crystal alloys consist of close-packed spectra of third-harmonic enhancement, along with
PMMA and PS spheres in an fcc crystalline structure the stopgaps, for pure PS (0%), 50% alloy, and pure
with 26% content of air. The refractive-index con- PMMA (100%). A nearly monotonic trend in the third-
trasts of these alloys, depending on the volume fraction harmonic enhancement factor as a function of composi-
of PMMA with respect to PS, will be 1.49 – 1.59. This tion is observed. In our laboratory we evaluated x 共3兲
refractive-index contrast is high enough to see a sig- for PS and PMMA and found it to be approximately
nificant directional gap. The calculated eeff for each 2.5 times larger for PS, which is expected because of
composition was used to determine the band structure the presence of p-conjugated units in PS.11 Thus our
of photonic crystal alloys, by the plane-wave expansion qualitative result of the third-harmonic enhancement
method. Finally, the stopgaps were calculated from factor for PS being approximately 2 – 2.5 times larger
the band structure. The f illing factor was assumed
to be 0.74. The calculated position of the bandgaps
is shown in Fig. 3. Excellent agreement is found
between the observed and the calculated values, con-
firming that an effective dielectric function of particles
is adequate to describe the photonic crystal alloys in
the case of small dielectric contrast. Within this limi-
tation, photonic crystal alloys provide a convenient
method of compositionally tuning the stopgap.
To investigate the role of scattering as a result of
compositional disorder we subtracted the sum of specu-
lar ref lectance and transmittance from unity (100%).
The difference was taken as an estimate of light losses
that were due to scattering. We assume that the ab-
sorption is equal to zero, because both materials (PS
and PMMA) do not have absorption bands in this spec-
tral region. The scattering shows a maximum for the
50% composition, which has the largest compositional
disorder. Fig. 3. Position of the stopgap center as a function of
One manifestation of impurities and defects in the PMMA concentration with respect to PS. The solid line
optical absorption of bulk semiconductors is a long- represents the theoretical values determined by using the
wavelength tail, known as an Urbach tail. This type effective dielectric function approach. The squares are
of defect-induced tail on the long-wavelength side of the experimental values.
2278 OPTICS LETTERS / Vol. 29, No. 19 / October 1, 2004

strength of scattering potential to introduce tailorable

impurity-induced manifestations. The use of photoni-
cally active components (such as dye-doped spheres) al-
lows one to conveniently create microcavities and study
cavity electrodynamics.
This work was supported at Buffalo by the Chem-
istry and Life Sciences Directorate of the U.S. Air
Force Office of Scientific Research through Defense
University Research Initiative on NanoTechnology
grant F496200110358. We thank Joseph Haus and
Nick Lepeshkin for their comments. P. N. Prasad’s
e-mail address is [email protected].

References
1. S. John, Phys. Rev. Lett. 58, 2486 (1987).
2. E. Yablonovitch, Phys. Rev. Lett. 58, 2059 (1987).
Fig. 4. Intensity of the generated third harmonic as a 3. P. N. Prasad, Nanophotonics (Wiley, New York, 2004).
function of wavelength. The dotted curves are the linear 4. J. Martorell, R. Vilaseca, and R. Corbalan, Appl. Phys.
transmission spectra of corresponding photonic crystal al- Lett. 70, 702 (1997).
loys. The values 0% and 100% correspond to pure PS and 5. P. P. Markowicz, H. Tiryaki, H. Pudavar, P. N. Prasad,
pure PMMA, respectively; 50% corresponds to 50% PS and N. N. Lepeshkin, and R. W. Boyd, Phys. Rev. Lett. 92,
50% to PMMA. 083903 (2004).
6. M. M. Sigalas, C. M. Soukoulis, C. T. Chan, and D.
Turner, Phys. Rev. B 53, 8340 (1996).
than that for PMMA, as can be seen from Fig. 4, is in 7. A. A. Asatryan, P. A. Robinson, L. C. Botten, R. C.
agreement with it. However, as the phase-matched McPhedran, N. A. Nicorovici, and C. M. de Sterke,
third-harmonic intensity is dependent on the square Phys. Rev. E 60, 6118 (1999).
8. A. A. Asatryan, P. A. Robinson, L. C. Botten, R. C.
of x 共3兲 and also has a term n共3v兲n3 共v兲 in the denomi-
McPhedran, N. A. Nicorovici, and C. M. de Sterke,
nator,13 one would expect the enhancement in PS to be Phys. Rev. E 62, 5711 (2000).
more than five times larger than that in PMMA. To 9. D. Zou, V. Derlich, K. Gandhi, M. Park, L. Sun, D.
quantitatively analyze this enhancement factor, one Kriz, Y. D. Lee, G. Kim, J. J. Aklonis, and R. Salovey,
needs to consider other factors such as the details of J. Polym. Sci. A 28, 1909 (1990).
band structure (refractive-index dispersion) for these 10. P. Jiang, J. F. Bertone, K. S. Hwang, and V. L. Colvin,
alloys and the local f ield enhancement factors.14 We Chem. Mater. 11, 2132 (1999).
plan to pursue a detailed study and analysis of the 11. R. J. Pradhan, I. I. Tarhan, and G. H. Watson, Phys.
nonlinear processes in these photonic crystal alloys. Rev. B 54, 13721 (1996).
In conclusion, photonic crystal alloys provide a con- 12. M. M. Sigalas, C. M. Soukoulis, C. T. Chan, R. Biswas,
and K. M. Ho, Phys. Rev. B 59, 12767 (1999).
venient medium to compositionally tune the bandgap
13. P. N. Prasad and D. J. Williams, Introduction to Non-
as well as the wavelength of a phase-matched nonlinear linear Optical Effects in Molecules and Polymers (Wi-
optical response. The photonic crystal alloy approach ley, New York, 1999).
also offers the opportunity to manipulate the dielec- 14. G. L. Fischer, R. W. Boyd, R. J. Gehr, S. A. Jenekhe,
tric contrast between the two components by chemical J. A. Osaheni, J. E. Sipe, and L. A. Weller-Brophy,
modif ication and processing and thus to control the Phys. Rev. Lett. 74, 1871 (1995).