In conventional luminescent solar concentrators (LSC) incident light is absorbed by luminophores and emitted
isotropically. Most of the emitted light is trapped inside the LSC by total internal reflection and guided to solar
cells at the edges. Light emitted towards the surfaces, however, is lost in the escape cone. Furthermore, when
the luminophore emits light in its absorption range, light is lost due to reabsorption. To overcome these losses,
we embed the luminescent material in photonic structures to influence the emission characteristics. Directional
and spectral redistribution of emission is supposed to enhance the light guiding in LSCs and reduce reabsorption
losses. For this purpose, we prepared opal films from PMMA colloids, in which Rhodamine B was embedded
during the polymerization process. In direction-resolved luminescence measurements a strong dependence of the
emitted spectrum on the detection direction was observed. Further, the light collection efficiency of the samples
was determined with optical measurements and light guiding due to the intended absorption and emission process
was observed. The overall performance, however, suffers from cracks and defects in the photonic crystal.
We present here the successful preparation of liquid crystalline core-shell elastomers via a microfluidic double-emulsion
process. The customized set-up allows for a temperature-controlled fabrication of the core-shell particles from a
thermoresponsive mesogenic monomer. The nematic liquid crystalline shell is filled with a non-mesogenic core of
silicone oil. To verify the core-shell structure with optical microscopy, we prepared particles with a colored core using a
red dye. We were also able to micro-manipulate the particles and penetrate them with a small glass capillary to extract
the liquid core.
Light management in single and tandem solar cells is becoming increasingly important to optimize the optical
and electro-optical properties of solar cells. After a short introduction to state-of-the-art light management
approaches, different applications of photonic crystals for photon management in solar cells are reviewed
and discussed concerning their applicability. Results on direction- and energy-selective filters for ultra-light-trapping,
intermediate reflectors for optimal current matching in tandem cells, and photonic crystal coating
for fluorescence collectors will be presented and discussed.
A 3D photonic intermediate reflector for textured micromorph silicon tandem solar cells has been investigated.
In thin-film silicon tandem solar cells consisting of amorphous and microcrystalline silicon with two junctions
of a-Si/c-Si, efficiency enhancements can be achieved by increasing the current density in the a-Si top cell
providing an optimized current matching at high current densities. For an ideal photon-management between
top and bottom cell, a spectrally-selective intermediate reflective layer (IRL) is necessary. We present the
first fully-integrated 3D photonic thin-film IRL device incorporated on a planar substrate. Using a ZnO
inverted opal structure the external quantum efficiency of the top cell in the spectral region of interest could
be enhanced. As an outlook we present the design and the preparation of a 3D self organized photonic crystal
structure in a textured micromorph tandem solar cell.
Fluorescent concentrators concentrate both diffuse and direct radiation without requiring tracking of the sun. In
fluorescent concentrators, luminescent materials embedded in a transparent matrix absorb sunlight and emit radiation
with a different wavelength. Total internal reflection traps the emitted light and guides it to solar cells attached to the
concentrator's edges. The escape cone of total internal reflection, however, limits the light collection efficiency.
Spectrally selective photonic structures, which transmit light in the absorption range of the luminescent material and
reflect the emitted light, reduce these losses. In this paper, we review different realizations of such structures and show
that they increase collection efficiency by 20%. However, light emitted into steep angles in respect to the front surface,
which would be lost without the photonic structures, has a very long effective path inside the concentrator until it reaches
a solar cell. Therefore it suffers from path length dependent losses. We discuss how emission into the unfavorable
directions can be suppressed by integrating the luminescent material into photonic structures, thus reducing these losses.
We present possible realizations both for the concentrator design and for the solar cells used in such systems.
We investigated a three dimensional inverted opal having the potential to notably increase light-trapping
in solar cells. The 3D photonic crystal top layer is an angle- and direction-selective filter, which decreases
the acceptance cone of the solar cell. Numerical optimisation methods are used to verify the optical and
electrical properties for a large angluar and energy spectrum for a system consisting of an inverted opal on
top of a thin crystalline silicon solar cell. It is numerically shown that an inverted opal grown in the Τ - Xdirection
might fulfill the requirement for such a filter. An estimate for the theoretically achievable efficiency
for nonconcentrated light is presented that do show an enchanced efficiency near the electronic band edge of
the absorber. The fabrication of first opals grown in Τ - Xdirection is presented and discussed with respect
to the quality and large scale fabrication.
In this paper we demonstrate the preparation of monodisperse particles from a liquid crystalline elastomer with a
preferred director orientation. For this we use a microfluidic setup to create droplets from a liquid crystalline
monomer which are polymerized in the liquid crystalline phase while flowing. When the obtained particles are
heated above the transition temperature of the nematic phase, they show a reversible shape change from
spherical to cigar-like. We show, that we can control the size as well as the polydispersity of these microactuators.
If the particles are prepared in non-flowing conditions, no or an undefined shape change is observed.
Particles polymerized in the isotropic phase show no shape deformation as well. Additionally we provide an
experimental proof for the stability of these structures versus acidic and basic conditions.
KEYWORDS: Silicon, Photonic crystals, Diffraction, Thin films, Photons, Absorption, Crystals, Thin film solar cells, Optical spheres, Tandem solar cells
We suggest an energy selective and diffractive optical element as intermediate layer in thin-film tandem solar cells. By
adjusting the lattice constant of this photonic crystal, we fitted the optical properties to match a silicon tandem pair. Our
device enhances the pathway of incident light within an amorphous silicon top cell in its spectral region of low
absorption. In this spectral overlap region of the tandem-junction's quantum efficiencies, photons are being transferred
towards the amorphous cell, which leads to an increase in the short-circuit current of the limiting top cell. From our
simulations we expect a current increase of 1.44mA/cm2 for an - amorphous/microcrystalline - silicon tandem cell,
corresponding to improvement of the tandem's absolute efficiency of about 1.3%.
We present a bottom-up approach for the construction of tunable functional defects in colloidal photonic crystals (CPCs). These structures incorporate polyelectrolyte multilayer (PEM) planar defects embedded in silica CPCs through a combination of evaporation induced self-assembly and microcontact transfer printing. We show how the enormous chemical diversity inherent to PEMs can be harnessed to create chemically active defect structures responsive to solvent vapor pressures, light, temperature as well as redox cycling. A sharp transmission state within the photonic stopband, induced by the PEM defect, can be precisely, reproducibly and in some cases reversibly tuned by these external stimuli. These materials could find numerous applications as optically monitored chemical sensors, adjustable notch filters and CPC-based tunable laser sources.
The possibility to create defined structures inside a synthetic opal is a key step towards applications in optics, where control of the propagation of light inside a photonic crystal is necessary. Here we report different methods for realizing defined embedded defects in opaline structures. Monodisperse colloids are synthesized by surfactant free emulsion polymerization of the acid labile monomer t-butyl-methacrylate (tBMA). The PtBMA colloids can be filled with sensitizer and photo acid generator and it is possible to crystallize them into photosensitive polymer opals. One method for the introduction of defects is a multilayer build-up of photo-labile (filled with photo acid generator) and photo-stable (not filled with photo acid generator) polymer beads. Irradiation through a mask with UV-light followed by baking and development with aqueous base allows subsequent patterning of the opaline film. Alternatively defects can be directly produced in the depth of an opal by two photon lithography. For this method a photo stable opal is infiltrated with ORMOCER, which is then polymerized. After removing the PtBMA opal an inverse opal structure is obtained. The holes are then filled with a resin and polymerization takes places at defined places via two photon lithography.
Spectra of the light scattered in the heterogeneous photonic crystal based on the thin triple-film opal, which was prepared by successive, convective force-assisted crystallisation of colloidal suspensions containing spheres of 374, 474 and again 374 nm in diameter, have been studied in the wavelength range of low order photonic bandgaps. If the ballistic regime of light propagation is preserved, the forward scattered light becomes the subject of the diffraction attenuation, whereas the backscattered light experiences both the diffraction enhancement and attenuation. A variety of possible configurations of scattered light measurements have been examined and corresponding spectra of scattered light have been compared with each other and with the spectra of transmitted and reflected light. The effect of the internal interfaces and the planar microcavity embedded in the photonic crystal upon the propagation of scattered light has been extracted.
We report on fabrication of high quality opaline photonic crystals from large silica spheres, self-assembled in hydrophilic trenches of silicon wafers by using a drawing apparatus with a combination of stirring. The achievements here reported comprise a spatial selectivity of opal crystallization without special treatment of the wafer surface, a filling of the trenches up to the top, leading to a spatially uniform film thickness, particularly an absence of cracks within the size of the trenches, and finally a good three-dimensional order of the opal lattice even in trenches with a complex confined geometry, verified using optical measurements. The opal lattice was found to match the pattern precisely in width as well as depth, providing an important step towards applications of opals in integrated optics. The influence of substrate structure on crystallization is also discussed.
Experimental and theoretical studies of the emission directionality diagrams of a perylene dye covering the inner surface of three-dimensional opal-based photonic crystals with incomplete photonic bandgap are reported. Directionality diagram of emission intensity is interpreted in terms of the spontaneous emission suppression by photonic band gap and the emission enhancement due to photon focusing phenomenon. A theoretical model is based on the classical analysis of an angular distribution of the radiated power of a point dipole.
The effect of photonic bandgap interface upon the light scattering was studied in hetero-opals consisting of two opal thin films with different lattice constant. It is shown that the weak scattering regime is preserved in thin hetero-opal films. By comparing scattering spectra of single and hetero-opal films recorded under reversing angles of light incidence and detection it was demonstrated that the interface scatters stronger the light at oblique incident angles. Squeezing of the scattering diagram of hetero-opals compared to single opal films is also assigned to the interface scattering.
A heterojunction between two 3-dimensional photonic crystals has been realized by interfacing two opal films of different lattice constants. The interface-related transmission minimum has been observed in the frequency range between two directional lowest-order bandgaps of the hetero-opal constituents. The interface transmission minimum has been modelled numerically and tentatively explained by formation of the standing wave across the photonic hetero-crystal due to matching of group velocities of optical modes in both parts at this frequency.
We probe the mesophase transitions and layer structures in thin ordered smectic liquid crystalline elastomer films by means of x-ray diffraction. Ordered elastomer films of submicrometer thickness are produced by crosslinking freely suspended smectic polymer films. After crosslinking - the mesomorphism is similar to that of the precursor polymer. The smectic layer spacing increases with temperature in the SmC* phase while it decays above the SmC*-SmA transition.
We review the status of 3D anisotropic crystals based on opal-semiconductor and opal-polymer nanocomposites with respect to controlling the spontaneous emission in space and frequency. An approach to grow photonic crystal structures form PMMA balls containing a laser dye is also presented. We show that depending mainly on the refractive index contrast and the choice of light emitter, photonic crystal effects manifest themselves in several forms. These are illustrated by choosing a suitable dopant for the polymer, such as laser dyes or rare-earth ions, under condition that their fluorescence should fall within the stop-band of the photonic crystals. The refractive index contrasts obtained are far from ideal and yet the impact of the anisotropic PBG is manifested unambiguously in, for example, the change of the density of states of photons and the directionality of the emission.
We describe new high Tg multi-functional polymers. In order to develop a photorefractive system with stable phase behavior at elevated temperatures we synthesized a series of maleimide/methyl vinyl isocyanate copolymers with carbazole as charge transporting moieties. We chose carbazole substituents attached with different spacer groups to adjust Tg of the polymers between 60 degrees C and 194 degrees C. As NLO chromophores we used hydroxyl alkyl functionalized 2- (N-ethyl-4-(4-nitrogen-phenylazo)-anilino)-ethanol and 2- (2,5-dimethyl-4-(4-nitro-phenylazo)-ethanol and 1-(4- ethylhydroxyphenyl)-3-methyl-4-(4-diethylaminophenyl)imino- pyrazole-5-on. Chromophore contents up to 44 mol percent have been attached under mild conditions by polymer analogous reactions. The materials are amorphous and posses excellent solubility in common solvents, e.g. chloroform and THF. Holographic four-wave mixing experiments was performed on a device made from a polymer elasticized such that the glass-transition temperature was Tg equals 80 degrees C. For the grating formation two exponential response times were found wit (tau) 1 equals 100 ms and (tau) 2 equals 1,5 s and a logarithmically weighted average response time of 200 ms.
The tricyanoquinodimethane group is one of the strongest (pi) -acceptors known to date. Yet it has not been employed as an acceptor in NLO chromophores with common aromatic (pi) -bridges. As an easily accessible example 7-(4-di-n- butylaminophenyl)-7,8,8-tricyanoquinodimethane is examined with respect to thermal/chemical stability and nonlinear optical efficiency. A derivative bearing an hydroxyethyl- spacer was synthesized and covalently attached to functionalized polyimides in a polymer analogous reaction. The second harmonic generation coefficients (d33) of the resulting nonlinear optical polymers were measured using the Maker-fringes experiment.
Fourier transform infrared spectroscopy of a ferroelectric liquid-crystalline material: 4-(3)-(S)- methyl-2-(S)-chloropentanoyloxy-4'-octyloxy-biphenyl has been investigated in the wavenumber range 450 - 4000 cm-1 for various temperatures and as a function of direct bias voltage in its SmC* phase. Samples prepared in both homeotropic and homogeneous alignments have been studied. The order parameter was calculated for several isolated IR vibrations which are characteristic of different parts and orientations of molecules. The dependence of the molecular tilt angle on direct bias voltage and temperature has similar characteristics to those obtained from electro-optic measurements.
KEYWORDS: Polymers, Chromophores, Glasses, Systems modeling, Polymerization, Carbonates, Chemical reactions, Nitrogen, Absorption, Temperature metrology
A new copolymer system with high, but still variable glass-transition temperatures was synthesized. The fixation of various NLO-chromophores is performed after the radical is performed after the radical copolymerization by a polymer analogous reaction. This was accomplished by copolymerizing various N-substituted maleimides with methylvinyl- or vinylisocyanate, so that a polymer with a 1:1 composition of the two monomers and reactive isocynate side-groups is obtained. With different substituents attached to the imide-ring, Tg can be adjusted between 100 and 200 degrees C. Two effects of the substituent at the imide-nitrogen are observed. Bulky gorups reduce the mobility of the chain and lead to high Tg values. A similar tendency is found for smaller less flexible substituents. In this case the intermolecular forces by hydrogen-bonding (urethanes) contibute ot the effects for high Tg's. A variety of different NLO-chromopores can be fixed on the polymer backbone by reaction of a hydroxyalkyl-spacer with the isocyanates, so that a urethane linkage between the chromophore and the polymer is formed. Based on the experience obtained with this first class of NLO-materials, new functionalized polymers were prepared. In order to further increase the Tg-values, while keeping a good processability (solubility), chemical modifications of the spin-coated polymer were prepared. In order to further increase the Tg-values, while keeping a good processablility (solubility), chemical modifications of the spin-coated polymer were performed. Monomers functionalized with tertiary butyl groups (esters or carbonates) allow it, to split off isobutene from the final (and processed) polymer, thereby reducing its solubility and increasing its Tg-value.
We have studied the pyroelectric behavior of both low molecular weight and polymeric ferroelectric liquid crystals. The alignment and electric quality of the pyroelectric LC samples is found to strongly influence the measured pyrosignal. The pyroelectric current is recorded as a function of temperature, and by a calibration procedure absolute values of the pyroelectric coefficient can be obtained. For a well-aligned siloxane copolymer FLC with high spontaneous polarization, a maximum value of about 13 nC/cm2.K for the pyroelectric coefficient was evaluated, comparable to values found for low-molar mass compounds.
Manfred Eich, Hanno Beisinghoff, Bengt Knoedler, Michael Ohl, Martin Sprave, Jan Vydra, M. Eckl, Peter Strohriegl, Michael Doerr, Rudolf Zentel, M. Ahlheim, M. Staehelin, B. Zysset, Julienne Liang, Regine Levenson, Joseph Zyss
Four high Tg side chain polymers have been investigated based on polyimide and acrylate backbones functionalized with DR1 and heterocyclic thiophene chromophores. UV-VIS studies revealed chromophore stability up to 210 degree(s)C. Maximum poling efficiency was found approximately 15 K above Tg. From dielectric relaxation studies and from poling dynamics it is obvious that chromophore reorientation follows an Arrhenius law at temperatures well above Tg leading into a WLF-behavior in the vicinity of Tg. Relaxation of the EO-coefficient could be interpreted in terms of a KWW function. The average relaxation times strongly deviate from the WLF-function at temperatures well below Tg and can be described with an Arrhenius law. Activation energies here are significantly smaller than those in the high temperature limit above Tg, indicating that the chromophore dipoles are incompletely coupled to the polymer (alpha) process. Very good stability was observed for the polyimide P3 with average relaxation times of 104 years at 50 degree(s)C and 4 months at 120 degree(s)C. EO coefficients of up to 12 pm/V at 1541 nm were realized using a poling field strength of 1 MV/cm. EO-coefficient at constant poling field was found to be approximately linearly dependent on chromophore content. Channeled waveguides were fabricated by selective reactive ion etching with small losses of 1 dB/cm at 1318 nm. However, loss varies strongly between 1 dB/cm and 3 dB/cm depending on film quality.
The collective and molecular dynamics of ferroelectric liquid crystalline side group polysiloxanes has been investigated for use of broadband dielectric spectroscopy (10-2 Hz - 109 Hz). In the lower frequency range (< 106 Hz) two collective relaxations, Goldstone- and soft-mode, could be observed. They are assigned to the fluctuations of the phase and the amplitude of the helical superstructure, respectively. In the high frequency regime (106 Hz - 109 Hz) one dielectric relaxation, the (beta) - relaxation, is found. It is assigned to the hindered rotation (libration) of the mesogene around its long molecular axis. It shows an Arrhenius-like temperature dependence with no deviations at the phase transition SA/S*C. A dilution of the mesogenes causes a decrease of the collectivity but remains the local dynamics uninfluenced.
A new method of preparing oriented NLO main chain polymers is presented. We synthesized NLO-monomers that consist of donor acceptor substituted tolane molecules that can be poled in the low molar mass state. In the oriented polar state these monomers can be chemically linked using a thermally activated polyaddition reaction. This reaction links the donor head of one monomer to the acceptor tail of the next hibiting bulk noncentrosymmetry with the average direction of the molecular dipoles parallel to the aligning field.
A crosslinkable side chain NLO-polymer of the bis-azobenzene type and an AB-type main chain NLO-polymer of the sulphonyl-tolane type have been synthesized and characterized with respect to their curing and electric poling properties. NLO-susceptibilities d33 of 11 pm/V and 7.5 pm/V, respectively, have been measured after initial relaxation and proved to be highly stable. During poling, transient SH-signal and square of poling current showed similar temporal behavior. Thus transient poling current can be considered to be a useful probe to monitor and to control the poling process. Direct current electrical conductivity was found to be strongly temperature dependent for both materials.
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