This PDF file contains the front matter associated with SPIE Proceedings Volume 9923, including the Title Page, Copyright information, Table of Contents, and Conference Committee listing.

In this work we investigate the mechanisms responsible for the energy level alignment at inorganic and organic semiconductors interfaces with photoelectron spectroscopy. We focus on the different contributions that lead to a substantial work function increase (up to 2.5 eV) when depositing thin layers of organic acceptor molecules [1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile (HATCN) and 2,2'-(perfluoronaphthalene-2,6- diylidene)dimalononitrile (F6-TCNNQ)] on two different inorganic semiconductors (ZnO and GaN). We discuss models to describe this work function increase, which take into account the role of bulk donor concentration of the inorganic semiconductors, their surface state density, and the distance between the inorganic semiconductor and the adsorbed molecules, and we emphasize the importance of surface states on the inorganic semiconductor. The absence of any adsorption-induced core level features for F6-TCNNQ indicates fractional charge transfer, in contrast to HATCN, where additional core level features indicate integer charge transfer. Finally, we demonstrate the utility of this interlayer approach by changing the energy level alignment between the showcase hybrid system ZnO/Sp6

It is crucial for the efficiency of photocatalytic reactions how to separate the photo-excited electrons and holes and how to utilize them at interfaces. There are two main difficulties to make these possible; variations of defects and co-catalysts. Most of the metal oxide photocatalysts have shallow and deep trap states, whose structure is always controversial. It is hard to tell which state helps reaction or not. Various co-catalysts have been applied, but also it is difficult to tell the real effect; charge separation or the surface passivation. Here, we will show the method to distinguish the defect type from the electron dynamics by using the transient grating (TG) method, which has a high sensitivity at the interface. We prepared a film sample by heating a TiO2 paste on a glass substrate. The film was contacted with a reactant solution sandwiched by another glass and a spacer. The TG method is one of the time-resolved techniques, which measures the refractive index change at the interface after shining a pulse excitation light. We could distinguish three different routes for photo-excited electrons; bulk trap (<100 ns), surface trap (1-5 us), Ti trap (0.5 – 10 s). Only the surface trap showed reactivity with reactants on the solution side. Ti trap had a longer lifetime, which was only observed when the photoexcited holes were scavenged. This trap seems to affect the cycle of the photocatalyst. This method offers simultaneous measurements of different trap states, and gives an insight of which defects have an actual reactivity.

Small organic molecules of the push-pull architecture are rapidly gaining their status in the organic electronics applications. In densely packed molecular films, both intra- and intermolecular interactions play an essential role for the device performance. Here we study two different molecules, a highly symmetric star-shaped one and its newly synthesized single arm analogue, for their photophysical properties. Both chromophores were dissolved in a solid matrix at different concentrations to vary their separation and therefore intermolecular coupling. We show that in both molecules the population relaxation accelerates by more than a factor of 10 at shorter intermolecular distances due to self-quenching thereby reducing the exciton survival time. The transient anisotropy dynamics are also quite similar, with their substantial acceleration at shorter interchromophore distances due to exciton diffusion caused by the Förster-like resonance energy transfer. However, the anisotropy values are noticeably lower for the star-shaped molecule because of intramolecular mixing of different polarization states. Finally, a model is presented that accounts for the observed results.

Recently, fluorescent Silicon (Si) Quantum Dots (QDs) have attracted much interest due to their high quantum yield, use of non-toxic and environmentally-benign chemicals, and water-solubility. However, more research is necessary to understand the energy level characteristics and single molecule behavior to enable their development for imaging applications. Therefore, single molecule time-resolved fluorescence spectroscopy of fluorescent Si QDs (cyan, green, and yellow) is needed. A rigorous analysis of time-resolved photon correlation spectroscopy and fluorescence lifetime data on single Si QDs at room temperature is presented.

We report on the use of time-resolved and polarised evanescent wave-induced fluorescence anisotropy measurements to probe molecular photophysics, motion and energy migration of fluorescent species in close proximity to a silica/film interface. In particular we show that the fluorescence decay and anisotropy of common fluorophores varies as a function of the plane of the fluorophore with respect to the interface, the distance from the interface, and as a function of position (using polarised EW imaging). We have applied time-resolved and polarised EW-induced fluorescence microspectroscopic measurements to dyes, thin polymer nanoparticle films and cells on silica surfaces, probing the variation in the photophysical dynamics within the films.

Resonance Raman Spectroscopy (RRS) is employed in this study to examine the influence of molecular weight on the optical response of a diketopyrrolopyrrole polymer (DPP-TT-T) in solution. The vibronic structure observed for the ground state absorption of this polymer is found to vary with molecular weight and solvent. Resonance Raman Intensity Analysis (RRIA) revealed that the absorption spectra can be described by at least two dipole-allowed transitions and the vibronic structure variation is due to differing contributions from linear and curved segments of the polymer.

Hamaker-Lifshitz constants are used to calculate van der Waals interaction forces between small particles in solution. Typically, these constants are size-independent and material specific. According to the Lifshitz theory, the Hamaker-Lifshitz constants can be calculated by taking integrals that include the dielectric permittivity, as a function of frequency, of the interacting particles and the medium around particles. The dielectric permittivity of interacting metal nanoparticles can be calculated using the free-electron Drude model for metals. For bulk metals, the Drude model does is size independent. However, the conducting electrons in small metal nanoparticles exhibit surface scattering, which changes the complex dielectric permittivity function. Additionally, the Drude model can be modified to include temperature dependence. That is, an increase in temperature leads to thermal volume expansion and increased phonon population, which affect the scattering rate of the electrons and the plasma frequency. Both of these terms contribute significantly to the Drude model for the dielectric permittivity of the particles. In this work, we show theoretically that scattering of the free conducting electrons inside noble metal nanoparticles with the size of 1 – 50 nm leads to size-dependent dielectric permittivity and Hamaker-Lifshitz constants. In addition, we calculate numerically the Hamaker-Lifshitz constants for a variety of temperatures. The results of the study might be of interest for understanding colloidal stability of metal nanoparticles.

High Q-factors and small mode volumes have made toroidal optical microresonators exquisite sensors to small shifts in the effective refractive index of the WGM modes. Eliminating contaminants and improving quality factors is key for many different sensing techniques, and is particularly important for photothermal imaging as contaminants add photothermal background obscuring objects of interest. Several different cleaning procedures including wet- and dry-chemical procedures are tested for their effect on Q-factors and photothermal background. RCA cleaning was shown to be successful in contrast to previously described acid cleaning procedures, most likely due to the different surface reactivity of the acid reagents used. UV-ozone cleaning was shown to be vastly superior to O₂ plasma cleaning procedures, significantly reducing the photothermal background of the resonator.

There is a growing demand to improve the operational lifetime of electroluminescent (EL) devices utilizing conjugated polymers which are often deposited over metal electrodes. Photo-degradation of the emissive organic layer is one factor that decreases the overall efficiency and longevity of these devices. Therefore, it is important to investigate the underlying photochemistry at metal-polymer interface. Here, effects of metal films on the emission properties of organic polymers are studied using total internal reflection fluorescence (TIRF) microscopy. It is observed that poly(phenylene vinylene) (MEHPPV) exhibits a remarkable increase in photo-stability when deposited on gold films relative to that on glass even in the presence of molecular oxygen and under continuous laser illumination. It is proposed that this interesting property is due to the surface plasmon of Au films.

Compact computational structure-function relations are needed to examine energy transfer between confined fields and carrier dynamics at heterostructure interfaces. This work used discrete dipole approximations to analyze quasiparticle excitation and dephasing at interfaces between metals and van der Waals materials. Simulations were compared with scanning transmission electron microscopy (STEM) for energy electron loss spectroscopy (EELS) at sub-nanometer resolution and femtosecond timescale. Artifacts like direct electron-hole pair generation were avoided. Comparing simulation with experiment distinguished quasiparticle energy transfer to hot carriers at the interface, and supported development of structure-function relations between interface morphology and emergent discrete and hybrid modes.

Research on carbon-based photocatalytic nanomaterials has been a field in continuous expansion in the last years. Graphene (or its derivatives) is currently one of the most studied materials due to its high surface area, photodegradation resistance, optical transparency and high charge mobility values. All of these excellent properties are highlighted for applications in various research areas. The incorporation of small amounts of reduced graphene oxide (RGO) sheets in semiconductors matrices is also a strategy widely used to improve the physicochemical properties, which cannot normally be achieved using conventional composites or pristine semiconductors. Most studies suggest that these twodimensional (2D) materials can facilitate electron injection and assist the electron transport in semiconductors. In this context, this manuscript will present examples of graphene-based semiconductor nanocomposites obtained by our research group and their application in the photodegradation of methylene blue (MB), photocatalytic conversion of CO₂ to hydrocarbon fuels and photocatalytic water splitting reaction. Our results show the positive effect of coupling the RGO sheets with semiconductors for photocatalysis.

In this paper two extremely narrow band-gap polymers, based on naturally occurring indigo with high thin film crystallinity, have been examined using transient absorption spectroscopy. This was done in order to assess their charge photogeneration and recombination characteristics in blends with PC₇₁BM. Two charge photogeneration mechanisms are found to be operating, depending on which component of the blend is photoexcited. Despite virtually isoenergetic LUMO levels, photoexcitation of the polymer causes standard electron transfer, albeit with a relatively low efficiency of 17 %. Photoexcitation of the fullerene, however, produces an exceptionally slow nanosecond timescale hole transfer.

Single-walled carbon nanotubes (SWCNT) are a promising material for future optoelectronic applications, including flexible electrodes and field-effect transistors. Molecular doping of carbon nanotube surface can be an effective way to control the electronic structure and charge dynamics of these material systems. Herein, two organic semiconductors with different energy level alignment in respect to SWCNT are used to dope the channel of the SWCNT-based transistor. The effects of doping on the device performance are studied with a set of optoelectronic measurements. For the studied system, we observed an opposite change in photo-resistance, depending on the type (electron donor vs electron acceptor) of the dopants. We attribute this effect to interplay between two effects: (i) the change in the carrier concentration and (ii) the formation of trapping states at the SWCNT surface. We also observed a modest ~4 pA photocurrent generation in the doped systems, which indicates that the studied system could be used as a platform for multi-pulse optoelectronic experiments with photocurrent detection.

Hybrid halide perovskites are at the frontier of optoelectronic research due to their excellent semiconductor properties and solution processability. For this reason, much attention has recently been focused on understanding photoexcited charge-carrier generation and recombination in these materials. Conversely, very few studies have so far been devoted to understanding carrier-carrier and carrier-phonon scattering mechanisms in these materials. This is surprising given that carrier scattering mechanisms fundamentally limit charge-carrier motilities and therefore the performance of photovoltaic devices. We apply linear polarization selective transient absorption measurements to polycrystalline CH3NH3PbBr3 hybrid halide perovskite films as an effective way of studying the scattering processes in these materials. Comparison of the photo induced bleach signals obtained when the linear polarizations of the pump and probe are aligned either parallel or perpendicular to one another, reveal a significant difference in spectral intensity and shape within the first few hundred femtoseconds after photoexcitation.

There is mounting evidence that long-range charge separation determines the efficiency of organic photovoltaic cells, yet different mechanisms remain under debate. One class of proposed mechanism is ultrafast coherent long-range charge separation, and another is a slower process whereby charges incoherently hop apart with a transiently enhanced mobility due to morphology and disorder. Here, we use transient absorption spectroscopy to probe incoherent charge separation dynamics in two different ways. First, we use a family of polymers whose backbone structures allows us to compare 2- phase donor-acceptor morphologies with 3-phase morphologies that feature an intermixed region. In the 3-phase system, we see pronounced spectral signatures associated with charges (holes) occupying the disordered intermixed region, and we track separation via biased charge diffusion to more ordered neat regions on the timescale of hundreds of picoseconds. Secondly, by resolving bimolecular charge recombination at high excitation density, we show that charge mobilities must be substantially enhanced on early timescales, which may be sufficient for separation to occur. Together, these measurements provide support for models of incoherent and relatively slow charge separation.

With the rising popularity of organic light-emitting diodes (OLEDs) in display applications, demand for more efficient blue emitters has increased. We have recently synthesized a novel blue-emitting, donor-acceptor system employing carbazole as the donor and a benzothiazole derivative as the acceptor, BTZ-CBZ. We find that the solution-phase emission of BTZ-CBZ is highly dependent on solvent polarity, both in lineshape and emission maximum, showing a Stokes shift of 50 nm in methylcyclohexane and 150 nm in acetonitrile. This is expected behavior for donor-acceptor compounds due to the presence of a charge-transfer excited state. However, the solid state properties are more important for OLED devices. Using time-dependent density functional theory calculations employing the linear-response (LR) and state-specific (SS) polarizable continuum model (PCM), we explore the effects of solvent reorganization on the emission properties of BTZ-CBZ. SS-PCM reproduces the solvatochromism behavior of BTZ-CBZ in solution, but LR-PCM shows effectively no shift with solvent polarity. We surmise that this is because solvent reorganization is necessary for the solvatochromic effect to occur. The effect of rigid matrices on the emission of BTZ-CBZ has direct implications on its viability as a blue emitter in solid-state OLEDs and which molecular environments will be ideal for devices.