This PDF file contains the front matter associated with SPIE Proceedings Volume 9939, including the Title Page, Copyright information, Table of Contents, Introduction (if any), and Conference Committee listing.

Photoinduced charge transfer is a key step in the mechanism of charge generation in organic solar cells. Charge transfer typically occurs from a photoexcited conjugated polymer donor to an electron acceptor. In an effort to better understand the primary events in solar cells, we have investigated photoinduced charge transfer in model donor-acceptor systems consisting of pi-conjugated oligomer donors that are covalently linked to diimide electron acceptors. These studies utilized oligo(thiophene), oligo(phenylene ethynylene) and oligo(fluorene) pi-conjugated systems with lengths varying from 4 to 12 repeat units linked to naphthalene diimide electron acceptors. Excitation with 100 femtosecond pulses at wavelengths correspoinding to the conjugated oligomer absorption band(s) leads to rapid photoinduced charge transfer to produce a charge separated state, (oligomer+)-(NDI-), which subsequently decays on timescales ranging from 100 ps to 5 ns. The dynamics of the forward and reverse electron transfer reactions depend strongly on the structure and length of the pi-conjugated oligomers, with the fastest rates occurring for oligo(thiophene)s, and considerably slower rates for oligo(phenylene ethynylene)s. The talk will discuss the structure-property relationships and energetic correlations that control the dynamics of charge separation and recombination.

A pseudo-symmetric two-photon absorbing dye (1) containing a central piperazine unit substituted with (benzothiazol-2- yl)-9,9-diethylfluoren-2-yl pendant groups has been synthesized and characterized. The molecule has a two-photonabsorption cross-section of σ₂ = 140 GM in tetrahydrofuran at ~ 740 nm and shows significant solvatochromism in the excited-state fluorescence spectra. The emission spectra broaden and the maxima bathochromically shift from 411 nm to 524 nm in n-hexane and acetonitrile, respectively. Moreover, the central piperazine moiety serves as a potential chelation site for ions. Addition of copper(I) hexafluorophosphate and zinc(II) triflate in acetonitrile indicate ground-state complexation with a shift in the emission maximum from 524 nm to 489 nm and 487 nm, respectively. Interestingly, the newly formed Cu and Zn complexes are more strongly emissive than the free dye. Finally, addition of p-toluenesulfonic acid in tetrahydrofuran also blue-shifts the emission maximum, but the intensity is quenched. Due to the photophysical changes induced by addition of metal ions and protons, the dye shows promise as a potential sensor.

In order to understand electronic and conformational effects on structure-spectroscopic property relationships in platinum acetylides, we synthesized a model series of chromophores trans-Pt(PBu₃)₂(CCPhenyl-X)₂, where X = NH₂, OCH₃, diphenylamino, t-Bu, methyl, H, F, benzothiazole, trifluoromethyl, CN and nitro. We collected linear spectra, including ground state absorption, phosphorescence and phosphorescence excitation spectra. We also performed DFT and TDDFT calculations on the ground and excited state properties of these compounds. The calculations and experimental data show the excited state properties are a function of the electronic properties of the substituents and the molecular conformation.

Strong coupling of plasmons and excitons can form hybrid states, the so called “plexcitons”. Especially with molecular J-aggregated dye molecules strong interaction becomes observable even under ambient conditions. In our work we investigate the nature of plexcitonic states formed in gold nanorods coated with a cyanine dye by transient absorption spectroscopy. We demonstrate that plexcitons show tunable plasmonic and excitonic non-linear optical behaviour. Our experimental data can be explained on the basis of a simple Lorentz oscillator model. We find that both the quality factor and the coupling strength between plasmons and excitons can be optically manipulated on an ultrashort time scale. T. Simon, D. Melnikau, A. Sánchez-Iglesias, M. Grzelczak, L. Liz-Marzán, Y. Rakovich, J. Feldmann and A. Urban, Exploring the optical non-linearities of plasmon-exciton hybrid resonances in coupled colloidal nanostructures, submitted (2016)

Organic electronics have been drawing a lot of attention over the past few decades with recent commercial applications such as organic photovoltaics, OLEDs, and flexible organic displays. One of the key components for designing organic molecules suitable for electronic devices is a fundamental understanding of excitonic behaviors. Here we report on the fabrication and photoluminescence studies of crystalline thin film organic alloy systems, metal free and metal based octabutoxyphthalocyanine (MOBPc_xH₂OBPc_1-x), and metal-free H₂OBPc and octabutoxynapthalocyanine (H₂OBNc) mixtures (H₂OBNc_xH₂OBPc_1-x). Crystalline thin films of these materials were deposited using an in-house developed pen writing technique that results in macroscopic long-range order even at the ratio of x = 0.5, which is unique and important for spectroscopic studies.

Our experiments reveal that the coherent excitonic states of MOBPc_xH₂OBPc_1-x and H₂OBNc_xH₂OBPc_1-x crystalline thin films can be tuned continuously as a function of alloy concentration (0 < x < 1). Moreover, the solution-processed technique used to fabricate these crystalline thin films provides us an unprecedented advantage in designing and controlling the bandgap tunability as well as achieving the desired exciton coherent length for variety of applications.

Photomigration in azo polymers is an area of research that witnessed intensive studies owing to its potential in optical manipulation; e.g. optical tweezing; the physical mechanism of which remains unsolved since its discovery about two decades ago. In this presentation, a detailed theoretical study that reproduces the phenomena associated with photomigration is presented, including the physical models and the associated master equations. I discuss polarization effects and I give the analytical solutions describing the steady-state and the dynamics of photomigration.

We have established that film morphology and laser induced heating from dye absorption are important parameters in the creation of new photonastic materials. Photonastic is defined as regular, repeatable movement in a pre-programmed direction following exposure to light. This work builds upon the development of photonastic polymers of ruthenium sulfoxide complexes, where the action of bending is ascribed to phototriggered isomerization of a sulfoxide ligand in a ruthenium coordination complex that is covalently attached to polynorbornene. The bending is analyzed in terms of a bilayer cantilever model.

This contribution focuses on a relatively old topic of azobenzene photomechanics, namely the photoinduced surface patterning. The phenomenon was demonstrated alreay in 1995, yet it has not redeemed its promise as a simple, one-step patterning method that could challenge the more conventional microfabrication techniques. However, inspired by recent advances in fabrication techniques, materials development, and theoretical modelling, the field is going through a revival from both fundamental and applied perspectives. (i) How much (or how little) azobenzene needed in order to create the surface patterns? (ii) What is the maximum size of objects that can be moved with light? (iii) Can one pattern crystalline materials? (iv) Under what conditions ss the patterning process light-reversible? These questions will herein be addressed via four case studies, all employing supramolecular materials where non-covalent intermolecular interactions are used to attach the azobenzenes into a passive host matrix. All azobenzene-based material movements are triggered by photoisomerization and are therefore inherently related to one another, and therefore we believe our observations to provide useful insights also for photomobile materials and photomechanical actuation.

We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that can serve as mechano-optic actuators for applications that include non-invasively steering fiber optics. The coil (polystyrene) end-blocks phase segregate from the liquid crystal midblock forming of uniform and uniformly-spaced physical crosslinks, resulting in highly reproducible and thermoreversible networks by self-assembly. These polymers are elastic in the melt (at room temperature) and can be easily spun, coated or molded. Mechanical stretching results in a temporary monodomain alignment. Starting from identical triblock prepolymers (with polystyerene end blocks and 1,2-polybutadiene midblocks), a matched pair (azobenzene-containing, and non-azobenzene-containing) of liquid crystal triblock copolymers was synthesized. These triblocks were then be blended to prepare a series of elastomers with 0 to 5% azobenzene groups, while matching in nearly all other physical properties (cross-link density, modulus, birefringence, etc.), allowing the effect of concentration of photo-responsive groups to be unambiguously determined. Results will be presented that demonstrate this approach to independent control of optical density and photo-mechanical sensitivity.

Electro-optic (EO) polymers are the promising material of choice for the waveguide modulation application due to their high EO coefficient, optical transparency, low dielectric loss, and compatibility with many materials and substrates. This widespread compatibility enables the construction of the unique hybrid polymer device to the silicon waveguide. One of the successful demonstrations in recent progress is the hybrid silicon modulator to the EO polymer. The hybrid silicon and polymer modulators have already demonstrated a very low half-wave voltage and multi-GHz bandwidth response. While, the fabrication is quite elaborate, involving the high-resolution lithography, controlled etching, and ion implantation process. In order to simplify the hybrid silicon and EO polymer modulator, we apply the conventional photolithography technique. The waveguide consists of silicon core with a thickness of 30 nm and a width of 2 m, and the cladding is the polymer. In such a thin silicon core, the side-wall scattering can be significantly reduced, thus the measured propagation loss of the waveguide is 1.5 dB/cm. The optical mode calculation reveals that 55% of the optical field extends into the polymer cladding. The hybrid phase modulator waveguide performed the half-wave voltage of the modulator to be 4.6 V at 1550 nm and excellent temperature stability at 85C for longer than 500 hours. We also investigate a mode converter which can couple the light from the hybrid polymer waveguide to the silicon strip waveguide. The coupling loss between two devices is measured to be 0.5 dB.

We report femtosecond light-induced macromolecular self-assembly (FLIMSA), which is observed when a high peak intensity femtosecond laser beam propagates through aqueous solution of pseudoisocyanine iodide (PIC) J-aggregates and induces the formation of 0.1 – 1.0 mm-size tube-like structure surrounding the laser beam, while at the same time allowing the beam to continue propagating without obstruction or scattering. The FLIMSA material is morphologically heterogeneous and gel-like and is formed at the margins rather than at the center of the beam. As a potential explanation of this effect we assume that the FLIMSA is induced by the high photon flux gradient characteristic of the femtosecond laser beam periphery. This hypothesis is corroborated by control experiments, where J-aggregate samples were illuminated with nanosecond laser sources with a varying pulse duration, power- and beam shape characteristics, but where no FLIMSA formation was observed.

Previously, we presented the experimental evidence for a degenerate frequency two beam coupling (TBC) in two photon absorbing (2PA) organic solutions. It has been well established that the two critical requirements for TBC are a nonlinear refractive index with a finite lifetime and that the interacting fields must have non-degenerate frequencies. However, degenerate frequency coupling has been shown for fields containing a time-dependent phase, i.e. a frequency chirp. This chirp can either be intrinsic to the fields or induced by self- and cross- phase modulation (S/XPM). For nanosecond pulses, the relatively small intrinsic chirp of the fields is negligible compared to the strong cumulative effects of population redistribution which generates large S/XPM. A S/XPM-mediated theoretical treatment for degenerate frequency TBC is presented along with numerical simulations using known nonlinear optical parameters to model the experimental results.

We studied the effects of two types of ultrasonic waves, shear waves and longitudinal waves, using two nonlinear optical techniques, second-harmonic generation and hyper-Rayleigh scattering. Since shear waves hardly propagate in liquids, their influence on molecules at the interface between a surface and a liquid was studied using second-harmonic generation. Longitudinal waves propagate easily in solution, thus we used hyper-Rayleigh scattering to probe the ultrasonic effects on chromophores in solution. While we did not find shear waves to alter the second-harmonic generation from chromophores at the liquid/surface interface, the longitudinal waves caused effects comparable to our earlier observations. Longitudinal ultrasound caused a strong intensity modulation of the nonlinear optical signal according to a wave-pattern.

Present-day methods for determining the performance of third-order nonlinear optical materials include Z-scan, degenerate four-wave mixing and third-harmonic generation (THG). All these techniques possess severe drawbacks; for example, in THG, since all media (air and glass walls of the cell) present a third-order effect, eliminating these contributions requires careful, complex analysis or use of vacuum chambers. We have developed nonlinear scattering as a sensitive, straightforward technique for determining the second hyperpolarizability of samples in solution. Herein, we will for the first time show the applicability of the technique to measure organometallic Ru-complexes, optimized for high nonlinear responses. The investigated compounds showed a significant second hyperpolarizability |γ|, ranging from 1.1 for the least efficient to 2.8 ∙ 10^-33 esu for the most efficient molecule, and comparable to fullerene C₆₀ in thin films. It was deemed infeasible to extract hyperpolarizabilities using a high-frequency femtosecond laser source by a modified z-scan setup, which, in contrast to nonlinear scattering, could not account for the high degree of thermal lensing present in the investigated compounds.

Current trends in technology development demand increased miniaturization and higher level integration of electronic and photonic components. Such needs arise in emerging imaging systems, optoelectronic devices, optical interconnects and photonic integrated circuits. Compact, integrated photonics requires high refractive index materials, which primarily comprise crystalline and amorphous semiconductors, as well as chalcogenide glasses, which can possess refractive indices higher than 4 and good infrared transparency. There is currently no high refractive index (n ~ 2 or above) that has the low cost production and ease of processing available in optical polymers. Such polymers would potentially cover applications that are not convenient or possible with crystalline and vitreous semiconductors. Examples of such applications include micro lens arrays for image sensors, optical adhesives for bonding and antireflection coatings, and high contrast optical waveguides. While much of the focus has been in the telecommunications transparency regions, significant new opportunities exist for a polymer which is capable of transmitting efficiently in the MWIR region. While there are polymers that have been synthesized with refractive indices as high as 1.75, these polymers are generally conjugated and incorporate heteroatoms such as sulfur or metals, and generally have complex and expensive syntheses. Here we report on new chalcogenide based copolymers with very high refractive index (n ~ 2) that also have good optical transmission properties in the near-, short- and mid-wave infrared up to 5µm. These polymers are rich in sulfur, have low hydrogen content and were made using inverse vulcanization.

We measured the diffraction efficiency response of two photorefractive polymer devices according to the duration of the single laser pulse used to record the hologram. The pulse duration was varied from 6 nanoseconds to 1 second, while the pulse energy density was maintained constant at 30 mJ/cm². This changed the peak power from 5 ×10⁹ mW to 30 mW. We observed a strong reciprocity failure of the efficiency according to the pulse duration, with a reduction as large as a factor 35 between 1 second and 30 μs pulse duration. At even lower pulse duration (< 30 μs), the efficiency leveled out and remained constant down to the nanosecond exposure time. The same behavior was observed for samples composed of the same material but with and without buffer layers deposited on the electrodes, and different voltages applied during the holographic recording. We explained these experimental results based on the charge transport mechanism involved in the photorefractive process. The plateau is attributed to the single excitation of the charge carriers by short pulses (τp < 30 μs). The increase of efficiency for longer pulse duration (τp > 30 μs) is explained by multiple excitations of the charge carriers that allows longer distance to be traveled from the excitation sites. This longer separation distance between the carriers increases the amplitude of the space-charge field, and improves the index modulation. The understanding of the response of the diffraction efficiency according to the pulse duration is particularly important for the optimization of photorefractive materials to be used at high refresh rate such as in videorate 3D display.

Sensing from the ultraviolet (UV)-visible to infrared (IR) is critical to environmental monitoring and remote sensing, fibre-optic communication, day and night-time surveillance, and emerging medical imaging modalities. Today, separate sensors or materials are required for different sub-bands within the UV to IR wavelength range. In general, AlGaN, Si, InGaAs and PbS based photodetectors (PDs) are used for the four important sub-bands: 0.25 μm-0.4 μm (UV), 0.45 μm-0.8 μm (visible), 0.9 μm-1.7 μm (near IR), 1.5 μm-2.6 μm (middle IR), respectively. To obtain the desired sensitivity, these detectors must be operated at low temperatures (for example, at 4.2 K). Thus, a “breakthrough” technology would be enabled by a new class of PDs ---- PDs that do not require cooling to obtain high detectivity; PDs which are fabricated by solution-processing to enable low-cost multi-color, high quantum efficiency, high sensitivity and high speed response over this broad spectral range. The availability of such PDs for use at room temperature (RT) would offer new and important applications. In this presentation, we would like to share with you how we approach RT operated ultrasensitive broad-band solution-processed PDs. - By developing novel low bandgap semiconducting polymers, we are able to develop RT operated solution-processed polymers PDs with spectral response from 350 nm to 1450 nm, the detectivity over 1013 Jones and linear dynamic range over 100 dB; spectral response from 350 nm to 2500 nm, the detectivity over 1012 Jones; - By using low bandgap semiconducting polymers mixed with high electrical conductivity PbS quantum dots (QDs), inverted polymer hybrid PDs with spectral response from 300 nm to 25000 nm, the detectivity over 1013 Jones and linear dynamic range over 100 dB are realized; - By using novel perovskite hybrid materials incorporated with carbon nanotubes, novel n-type newly developed semiconducting polymers, we are able to realize RT operated solution-processed PDs with spectral response from 350 nm to 1400 nm, the detectivity over 1012 Jones and linear dynamic range approximatively 100 dB.

Although the detection of photons is ubiquitous, man-made photon detectors still limits the effectiveness of applications such as light/laser detection, photography, astronomy, quantum information science, medical imaging, microscopy, communications, and others. The performance of the technologically most advanced detectors based on CMOS semiconductor technology has improved during the last decades but at the detriment of increased complexity, higher cost, limited portability and compactness, and limited area. On the other hand, nature has produced a relatively simple detector with remarkable properties: the human eye. The exploration of new paradigms in photon detection using new material platforms might therefore provide a path to further challenge the frontiers of applications enabled by light. In this talk, we will report on the realization of solution-processed organic semiconductor visible spectrum photodetectors with a high specific detectivity above 1014 Jones, at least an order of magnitude larger than values found in photodiodes based on silicon. These detectors demonstrate a sub-pA current under reverse bias in the dark, making them suitable for detecting very low levels of light. The small dark current under reverse bias allows the characterization of these devices over 9 orders of magnitude of increasing light irradiance. The detectors are based on the device structure: tin-doped indium oxide / ethoxylated polyethylenimine / poly(3-hexylthiophene) : indene C60 bisadduct / molybdenum oxide / silver and present a path toward fabrication on flexible substrates. We will show that these detectors can operate over a large dynamic range in the self-powered photovoltaic mode where the light produces a photovoltage that can be measured directly without any external bias source. We believe that large-area flexible photodetectors with detectivity values comparable to or better than those displayed by silicon-based photodiodes will enable a wide variety of applications from the detection of radiation to non-planar imaging arrays.

In modern electronic systems memory elements are of fundamental importance for data storage. Especially solution-processable nonvolatile organic memories, which are inexpensive and can be manufactured on flexible substrates, are a promising alternative to brittle inorganic devices. Organic photochromic switchable compounds, mostly dithienylethenes (DTEs), are thermally stable, fatigue resistant and can undergo an electrically- or/and photo-induced ring-opening and -closing reaction which results in a change of energy levels. Due to the energetic difference in the highest occupied molecular orbital (HOMO) between the open and closed isomer, the DTE layer can be exploited as a switchable hole injection barrier that controls the electrical current in the diode. We demonstrated that a light-emitting organic memory (LE-OMEM) device with a perfluoro DTE transduction layer can be switched electrically via high current densities pulses and optically by irradiated light, with impressive current ON/OFF Ratios (OOR) of 10Λ2, 10Λ4 respectively. Currently we aim to minimize the barrier of the ON state and maximize the barrier of the OFF state by designing DTE molecules with larger differences in the HOMO energies of the two isomers yielding improved OOR values. By synthesizing perhydro derivates of DTE we achieved molecules with high HOMO levels and large ΔHOMO energies providing OMEM devices with excellent physical properties (OOR 1.4 x higher than perfluoro DTE). Due to the high HOMO level of the perhydro DTE utilization of hole transport layers (HTLs) is not necessary and thus manufacturing of OMEM devices is simplified.

Tunable waveguide Bragg gratings were demonstrated in PYR-3 chromophore doped polymers. We report on the fabrication and the performance of the device. Polycarbonate thin films were doped with PYR-3 (2-{3- Cyano-4- [3-(1-decyl-1 H-pyridin-4-ylidene)-propenyl]-5,5-dimethyi-5 H-furan-2-ylidene}-malononitrile) chromophore, consisting of a dihydropyridinylidene donor and three carbon atoms in the conjugated linker between donor and acceptor. Ridge waveguides were laser micro-machined into the polycarbonate film with a JPSA micromachining system equipped with a KrF excimer laser at 248 nm. Bragg gratings were inscribed into the waveguide by permanently photobleaching the PYR-3 chromophores using a phase mask to achieve narrowband reflections at wavelengths around 1550 nm. Electro-optic properties were introduced by contact poling. Applying a static external electric field leads to the shift of the reflection peak.

Faraday rotation is a magneto-optic phenomenon in which the polarization plane of light is rotated due to magnetically induced circular birefringence. It can be used in a variety of applications such as optical isolators, magnetic field sensors and current sensors. So far, most of the applications use inorganic, paramagnetic materials, which have Verdet constants up to millions of degrees per tesla per meter in the visible spectrum range. They are performant at telecommunication wavelengths, though with smaller Verdet constants, so thicker materials are used. Disadvantages of these materials are their magnetic saturation at low magnetic fields and their strong temperature dependency. Organic, diamagnetic materials on the contrary, saturate at much larger magnetic fields and are less temperature dependent. Furthermore, they also have the advantage of their flexibility and processability. Up to now, magneto-optical research on organic materials has mostly characterized materials with low magneto-optical activity in regions without absorption, but there are some exceptions. Some pi-conjugated polymers have been shown to have very large magneto-optic responses. Furthermore, a mesogenic, organic molecule has been reported with a very high Verdet constant. Conclusive explanations for these large Verdet constants are still lacking, but different possible hypotheses were proposed. In our ongoing search for organic materials with exceptional magneto-optical properties, we examined conjugated, rod-like molecules. Structural, these molecules show close resemblances with the earlier reported mesogenic, organic molecule. We measured giant Verdet constants for thin films of these molecules, reaching values almost as giant as the previous reported mesogenic molecule. These findings shed first preliminary light on a structure-activity relationship for giant Faraday rotation in diamagnetic organic materials.

This work presents different polymer diffusing films for optical components. In optical applications it is sometimes important to have a film with an adjusted refractive index, scattering properties and a low surface roughness. These diffusing films can be used to increase the efficiency of optical components like organic light emitting diodes (OLEDs). In this study three different epoxy acrylate mixtures containing Syntholux 291 EA, bisphenol a glycerolate dimethacrylate, Sartomer SR 348 L are characterized and optimized with different additives. The adjustable refractive index of the material is achieved with a chemical doping by 9-vinylcarbazole. Titanium nanoparticles in the mixtures generate light scattering and increase the refractive index additionally. To prevent sedimentation and agglomeration of these nanoparticles, a stabilization agent [2-(2-methoxyethoxy)ethoxy]acetic acid is added to the mixture. Other ingredients are a UV-starter and thermal starter for the radical polymerization. A high power stirrer (ultraturrax) is used to mix and disperse all chemical substances together to a homogenous mixture. The viscosity behavior of the mixtures is an important property for the selection of the production method and gets characterized.

After the mixing, the monomer mixture is applied on glass substrates by blade coating or screen printing.

To initiate the chain growing (polymerization) the produced films are irradiated for 10 minutes long with UV light (UV LED Spot Hönle, 405 nm). After this step a final post bake from the layers in the oven (150°C, 30 min.) is operated.

Light transmission measurements (UV-Vis) of the polymer matrix and roughness measurements complement the characterization.

Main optical, thermal and mechanical properties of new compositions based on alicyclic polyimide and active bright red 6C synthetic dye have been studied. It was shown that the transmission ratio of the new material in the region of 400-900 nm and 2.0 wt.% dye concentration was around 60-70%. Thermal, mechanical and electrical properties of new colored compositions were comparable with the properties of original polyimide.

Bulk, transparent organic nonlinear optical (NLO) single-crystals of imidazolium L-Ascorbate (ImLA) were grown using slow-evaporation. Crystal structure was determined by single crystal X-ray diffraction analysis. Preliminary linear optical measurements through UV-Visible and infrared spectroscopy revealed good optical transmittance and a low near-UV cutoff wavelength at 256 nm. Kurtz and Perry powder test revealed that ImLA is a phase-matchable NLO material with a second harmonic generation (SHG) efficiency of 1.2 times larger than that of standard KH₂PO₄ (KDP). Laser damage thresholds were determined for ImLA.