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This roadmap includes the perspectives and visions of leading researchers in the key areas of flexible and printable electronics. The covered topics are broadly organized by the device technologies (sections 1–9), fabrication techniques (sections 10–12), and design and modeling approaches (sections 13 and 14) essential to the future development of new applications leveraging flexible electronics (FE). The interdisciplinary nature of this field involves everything from fundamental scientific discoveries to engineering challenges; from design and synthesis of new materials via novel device design to modelling and digital manufacturing of integrated systems. As such, this roadmap aims to serve as a resource on the current status and future challenges in the areas covered by the roadmap and to highlight the breadth and wide-ranging opportunities made available by FE technologies.

Perovskite solar cells (PSC) are promising potential competitors to established photovoltaic technologies due to their superior efficiency and low-cost solution processability. However, the limited understanding of the crystallization behaviour hinders the technological transition from lab-scale cells to modules. In this work, advanced phase field (PF) simulations of solution-based film formation are used for the first time to obtain mechanistic and morphological information that is experimentally challenging to access. The well-known transition from a film with many pinholes, for a low evaporation rate, to a smooth film, for high evaporation rates, is recovered in simulation and experiment. The simulation results provide us with an unprecedented understanding of the crystallization process. They show that supersaturation and crystallization confinement effects determine the final morphology. The ratio of evaporation to crystallization rates turns out to be the key parameter driving the final morphology. Increasing this ratio is a robust design rule for obtaining high-quality films, which we expect to be valid independently of the material type.

Reliable fabrication of large-area perovskite films with antisolvent-free printing techniques requires high-volatility solvents, such as 2-methoxyethanol (2ME), to formulate precursor inks. However, the fabrication of high-quality cesium-formamidinium (Cs-FA) perovskites has been hampered using volatile solvents due to their poor coordination with the perovskite precursors. Here, this issue is resolved by re-formulating a 2ME-based Cs 0.05 FA 0.95 PbI 3 ink using pre-synthesized single crystals as the precursor instead of the conventional mixture of raw powders. The key to obtaining high-quality Cs-FA films lies in the removal of colloidal particles from the ink and hence the suppression of colloid-induced heterogeneous nucleation, which kinetically facilitates the growth of as-formed crystals toward larger grains and improved film crystallinity. Employing the precursor-engineered volatile ink in the vacuum-free, fully printing processing of solar cells (with carbon electrode), a power conversion efficiency (PCE) of 19.3%, a T 80 (80% of initial PCE) of 1000 h in ISOS-L-2I (85 °C/1 Sun) aging test and a substantially reduced bill of materials are obtained. The reliable coating methodology ultimately enables the fabrication of carbon-electrode mini solar modules with a stabilized PCE of 16.2% (average 15.6%) representing the record value among the fully printed counterparts and a key milestone toward meeting the objectives for a scalable photovoltaic technology., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Despite the great success of perovskite photovoltaics in terms of device efficiency and stability using laboratory-scale spin-coating methods, the demand for high-throughput and cost-effective solutions remains unresolved and rarely reported because of the complicated nature of perovskite crystallization. In this work, we propose a stable precursor ink design strategy to control the solvent volatilization and perovskite crystallization to enable the wide speed window printing (0.3 to 18.0 m/min) of phase-pure FAPbI 3 perovskite solar cells (pero-SCs) in ambient atmosphere. The FAPbI 3 perovskite precursor ink uses volatile acetonitrile (ACN) as the main solvent with DMF and DMSO as coordination additives is beneficial to improve the ink stability, inhibit the coffee rings, and the complicated intermediate FAPbI 3 phases, delivering high-quality pin-hole free and phase-pure FAPbI 3 perovskite films with large-scale uniformity. Ultimately, small-area FAPbI 3 pero-SCs (0.062 cm 2 ) and large-area modules (15.64 cm 2 ) achieved remarkable efficiencies of 24.32 % and 21.90 %, respectively, whereas the PCE of the devices can be maintained at 23.76 % when the printing speed increases to 18.0 m/min. Specifically, the unencapsulated device exhibits superior operational stability with T 90 >1350 h. This work represents a step towards the scalable, cost-effective manufacturing of perovskite photovoltaics with both high performance and high throughput., (© 2023 Wiley-VCH GmbH.)

In the present work, an insight on the morpho/structural properties of semitransparent organic devices for buildings' integrated photovoltaics is presented, and issues related to interface and bulk stability are addressed. The organic photovoltaic (OPV) cells under investigation are characterized by a blend of PM6:Y6 as a photo-active layer, a ZnO ETL (electron transporting layer), a HTL (hole transporting layer) of HTL-X and a transparent electrode composed by Ag nanowires (AgNWs). The devices' active nanomaterials, processed as thin films, and their mutual nanoscale interfaces are investigated by a combination of in situ Energy Dispersive X-ray Reflectometry (EDXR) and ex situ Atomic Force Microscopy (AFM), X-ray Diffraction (XRD) and micro-Raman spectroscopy. In order to discriminate among diverse concomitant aging pathways potentially occurring upon working conditions, the effects of different stress factors were investigated: light and temperature. Evidence is gained of an essential structural stability, although an increased roughness at the ZnO/PM6:Y6 interface is deduced by EDXR measurements. On the contrary, an overall stability of the system subjected to thermal stress in the dark was observed, which is a clear indication of the photo-induced origin of the observed degradation phenomenon. Micro-Raman spectroscopy brings light on the origin of such effect, evidencing a photo-oxidation process of the active material in the device, using hygroscopic organic HTL, during continuous illumination in ambient moisture conditions. The process may be also triggered by a photocatalytic role of the ZnO layer. Therefore, an alternative configuration is proposed, where the hygroscopic HTL-X is replaced by the inorganic compound MoOx. The results show that such alternative configuration is stable under light stress (solar simulator), suggesting that the use of Molybdenum Oxide, limiting the photo-oxidation of the bulk PM6:Y6 active material, can prevent the cell from degradation.

Organic photovoltaics (OPVs) have progressed steadily through three stages of photoactive materials development: (i) use of poly(3-hexylthiophene) and fullerene-based acceptors (FAs) for optimizing bulk heterojunctions; (ii) development of new donors to better match with FAs; (iii) development of non-fullerene acceptors (NFAs). The development and application of NFAs with an A-D-A configuration (where A = acceptor and D = donor) has enabled devices to have efficient charge generation and small energy losses ( E loss < 0.6 eV), resulting in substantially higher power conversion efficiencies (PCEs) than FA-based devices. The discovery of Y6-type acceptors (Y6 = 2,2'-((2 Z ,2' Z )-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]-thiadiazolo[3,4- e ]-thieno[2″,3″:4',5']thieno-[2',3':4,5]pyrrolo-[3,2- g ]thieno-[2',3':4,5]thieno-[3,2- b ]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1 H -indene-2,1-diylidene))dimalononitrile) with an A-DA' D-A configuration has further propelled the PCEs to go beyond 15% due to smaller E loss values (∼0.5 eV) and higher external quantum efficiencies. Subsequently, the PCEs of Y6-series single-junction devices have increased to >19% and may soon approach 20%. This review provides an update of recent progress of OPV in the following aspects: developments of novel NFAs and donors, understanding of the structure-property relationships and underlying mechanisms of state-of-the-art OPVs, and tasks underpinning the commercialization of OPVs, such as device stability, module development, potential applications, and high-throughput manufacturing. Finally, an outlook and prospects section summarizes the remaining challenges for the further development of OPV technology.

In solution processing of thin films, the material layer is deposited from a solution composed of several solutes and solvents. The final morphology and hence the properties of the film often depend on the time needed for the evaporation of the solvents. This is typically the case for organic photoactive or electronic layers. Therefore, it is important to be able to predict the evaporation kinetics of such mixtures. We propose here a new phase-field model for the simulation of evaporating fluid mixtures and simulate their evaporation kinetics. Similar to the Hertz-Knudsen theory, the local liquid-vapor (LV) equilibrium is assumed to be reached at the film surface and evaporation is driven by diffusion away from this gas layer. In the situation where the evaporation is purely driven by the LV equilibrium, the simulations match the behavior expected theoretically from the free energy: for evaporation of pure solvents, the evaporation rate is constant and proportional to the vapor pressure. For mixtures, the evaporation rate is in general strongly time-dependent because of the changing composition of the film. Nevertheless, for highly nonideal mixtures, such as poorly compatible fluids or polymer solutions, the evaporation rate becomes almost constant in the limit of low Biot numbers. The results of the simulation have been successfully compared to experiments on a polystyrene-toluene mixture. The model allows to take into account deformations of the liquid-vapor interface and, therefore, to simulate film roughness or dewetting.

The performance of solution-processed solar cells strongly depends on the geometrical structure and roughness of the photovoltaic layers formed during film drying. During the drying process, the interplay of crystallization and liquid-liquid demixing leads to structure formation on the nano- and microscale and to the final rough film. In order to better understand how the film structure can be improved by process engineering, we aim at theoretically investigating these systems by means of phase-field simulations. We introduce an evaporation model based on the Cahn-Hilliard equation for the evolution of the fluid concentrations coupled to the Allen-Cahn equation for the liquid-vapour phase transformation. We demonstrate its ability to match the experimentally measured drying kinetics and study the impact of the parameters of our model. Furthermore, the evaporation of solvent blends and solvent-vapour annealing are investigated. The dry film roughness emerges naturally from our set of equations, as illustrated through preliminary simulations of spinodal decomposition and film drying on structured substrates.

Colloidal nanocrystals from PbS are successfully applied in highly sensitive infrared photodetectors with various device architectures. Here, we demonstrate all-printed devices with high detectivity (∼10 12 cm Hz 1/2 /W) and a cut-off frequency of >3 kHz. The low material consumption (<0.3 mg per detector) and short processing time (14 s per detector) enabled by the automated printing promises extremely low device costs. To enable all-printed devices, an ink formulation was developed based on nanocrystals stabilized by perovskite-like methylammonium iodobismuthate ligands, which are dispersed in a ternary solvent. Fully inkjet printed devices based on this solvent were achieved with printed silver electrodes and a ZnO interlayer. Considerable improvements were obtained by the addition of small amounts of the polymer poly(vinylpyrrolidone) to the ink. The polymer improved the colloidal stability of the ink and its film-formation properties and thus enabled the scalable printing of single detectors and detector arrays. While photoconductors were shown here, the developed ink will certainly find application in a series of further electronic devices based on nanocrystals from a broad range of materials.

A novel main-chain polyfullerene, poly[fullerene-alt-2,5-bis(octyloxy)terephthalaldehyde] (PPC4), is investigated for its hypothesized superior morphological stability as an electron-accepting material in organic photovoltaics relative to the widely used fullerene phenyl-C61-butyric acid methyl ester (PCBM). When mixed with poly(3-hexylthiophene-2,5-diyl) (P3HT), PPC4 affords low-charge-generation yields because of poor intermixing within the blend. The adoption of a multiacceptor system, by introducing PCBM into the P3HT:polyfullerene blend, was found to lead to a 3-fold enhancement in charge generation, affording power conversion efficiencies very close to that of the prototypical P3HT:PCBM binary control. Upon thermal stressing and in contrast to the P3HT:PCBM binary, photovoltaic devices based on the multiacceptor system demonstrated significantly improved stability, outperforming the control because of suppression of the PCBM migration and aggregation processes responsible for rapid device failure. We rationalize the influence of the fullerene miscibility and its implications on the device performance in terms of a thermodynamic model based on Flory-Huggins solution theory. Finally, the potential universal applicability of this approach for thermal stabilization of organic solar cells is demonstrated, utilizing an alternative low-band-gap polymer-donor system.

The technology behind a large area array of flexible solar cells with a unique design and semitransparent blue appearance is presented. These modules are implemented in a solar tree installation at the German pavilion in the EXPO2015 in Milan/IT. The modules show power conversion efficiencies of 4.5% and are produced exclusively using standard printing techniques for large-scale production.

The kinetics of photodegradation and the reactivity of different sites of the low-band-gap polymers poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (C-PCPDTBT) and poly[2,6-(4,4-bis-(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-alt-4,7-(2,1,3-benzothiadiazole)] (Si-PCPDTBT) are investigated as thin films and are compared to those of poly(3-hexylthiophene) (P3HT). The decay kinetics are monitored with UV/Vis spectroscopy and the reactivity and product evolution are investigated with X-ray photoelectron spectroscopy (XPS). Both polymers exhibit higher stability than P3HT. The bridging atom in the cyclopentadithiophene (CPDT) subunit has a significant influence on the stability. Varying oxidation rates for the different elements were observed. In the case of Si-PCPDTBT, the silicon atom is oxidized primarily, whereas the photooxidation rates of the other elements are reduced relative to C-PCPDTBT. Additionally, XPS experiments with varying excitation energies reveal a significant reaction gradient within a few nanometers of the surface of degraded thin films of C-PCPDTBT., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Understanding the stability and degradation mechanisms of organic solar materials is required to achieve long device lifetimes. Here we study photodegradation mechanisms of the (poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]):[6,6]-phenyl-C61-butyric acid methyl ester (PCPDTBT:PCBM) low band gap-based photovoltaic blend. We apply quasi steady state Photo-induced Absorption Optical Spectroscopy, time-resolved Electron Spin Resonance Spectroscopy and theoretical modeling to investigate the dynamics of long-lived photoexcited species. The role of the interfacial physics in the efficiency and robustness of the photovoltaic blend is clarified. We demonstrate that the polymer triplet state (T), populated through the interfacial charge transfer (CT) state recombination, coexists with charge carriers. However, in contrast to previous suggestions, it has no role in the degradation process caused by air exposure. Instead, the long-lived emissive interfacial CT state is responsible for the blend degradation in air. It mediates direct electron transfer to contaminants, leading to the formation of reactive and harmful species, such as the superoxide.

Recently, the concept of near-infrared sensitization is successfully employed to increase the light harvesting in large-bandgap polymer-based solar cells. To gain deeper insights into the operation mechanism of ternary organic solar cells, a comprehensive understanding of charge transfer-charge transport in ternary blends is a necessity. Herein, P3HT:PCPDTBT:PCBM ternary blend films are investigated by transient absorption spectroscopy. Hole transfer from PCPDTBT-positive polarons to P3HT in the P3HT:PCPDTBT:PCBM 0.9:0.1:1 blend film can be visualized. This process evolves within 140 ps and is discussed with respect to the proposed charge-generation mechanisms., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The standard picture of photovoltaic conversion in all-organic bulk heterojunction solar cells predicts that the initial excitation dissociates at the donor/acceptor interface after thermalization. Accordingly, on above-gap excitation, the excess photon energy is quickly lost by internal dissipation. Here we directly target the interfacial physics of an efficient low-bandgap polymer/PC(60)BM system. Exciton splitting occurs within the first 50 fs, creating both interfacial charge transfer states (CTSs) and polaron species. On high-energy excitation, higher-lying singlet states convert into hot interfacial CTSs that effectively contribute to free-polaron generation. We rationalize these findings in terms of a higher degree of delocalization of the hot CTSs with respect to the relaxed ones, which enhances the probability of charge dissociation in the first 200 fs. Thus, the hot CTS dissociation produces an overall increase in the charge generation yield.

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (η=8%). π-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.

The effect of the additive 1,8-octanedithiol (ODT) on the nanometer-scale morphology and local photophysical properties of low-bandgap polymer blends of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b'] dithiophene)- alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl C(61) -butyric acid methyl ester (PCBM) is investigated. Phase separations of the PCPDTBT:PCBM blend film induced by ODT are visualized by the morphological changes from fibril-shaped features to spherical bumps, by the dramatically increased photoluminescence emission from PCPDTBT that was originally largely quenched, and by the fluctuations of spectral features at different locations of the sample surface. The correlations between the morphology and the local photophysical properties of the blend film with/without ODT at both the micrometer and nanometer scales are revealed by confocal and high-resolution near-field spectroscopic mapping techniques., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Partially deuterated 1,4-distyrylbenzene () is included into the pseudohexagonal nanochannels of perhydrotriphenylene (PHTP). The overall and intramolecular mobility of is investigated over a wide temperature range by (13)C, (2)H NMR as well as fluorescence spectroscopy. Simulations of the (2)H NMR spectral shapes reveal an overall wobble motion of in the channels with an amplitude of about 4 degrees at T = 220 K and 10 degrees at T = 410 K. Above T = 320 K the wobble motion is superimposed by localized 180 degrees flips of the terminal phenyl rings with a frequency of 10(6) Hz at T = 340 K. The activation energies of both types of motions are around 40 kJ mol(-1) which imply a strong sterical hindrance by the surrounding PHTP channels. The experimental vibrational structure of the fluorescence excitation spectra of is analyzed in terms of small amplitude ring torsional motions, which provide information about the spatial constraints on by the surrounding PHTP host matrix. Combining the results from NMR and fluorescence spectroscopy as well as of time-dependent density functional calculations yields the complete potential surfaces of the phenyl ring torsions. These results, which suggest that intramolecular mobility of is only reduced but not completely suppressed by the matrix, are corroborated by MD simulations. Unrealistically high potential barriers for phenyl ring flips are obtained from MD simulations using rigid PHTP matrices which demonstrate the importance of large amplitude motions of the PHTP host lattice for the mobility of the guest molecules.

We characterize photoinduced charge injection at the interface between a fluorinated copper phthalocyanine (CuPcF(16)) film deposited over a GaAs(100) wafer by means of pump-probe spectroscopy combined with ultraviolet photoemission spectroscopy (UPS) and electromodulated transmission spectroscopy. UPS characterization of the hybrid interface demonstrates that the CuPcF(16) 's lowest unoccupied molecular level (LUMO) is almost aligned with the GaAs conduction band. Upon photoexcitation of the hybrid interface with 150 fs pulses we observe an efficient photoinduced electron transfer from CuPcF(16) to GaAs. The evolution of interfacial CuPcF(16) charges appear to be strongly influenced by energy level alignment at the GaAs/CuPcF(16) heterojunction.

We present a combined experimental and theoretical study on energy transfer processes in a well-defined three-dimensional host-guest system, which allows for high chromophore concentrations while maintaining the highly luminescent properties of the molecules in solution. The self-assembled, nanostructured system with a defined ratio of included donor and acceptor molecules is amenable to quantitative comparison between experiment and theory. Experimentally, energy migration is monitored by steady-state and time-resolved fluorescence spectroscopy. From the theoretical side, the energy transfer process is modeled by a Monte Carlo approach including homo and hetero transfer steps with multi-acceptor distribution. In this dense system, the classical Förster point-dipole approach for energy transfer breaks down, and the hopping rates are therefore calculated on the basis of a quantum-chemical description of the donor and acceptor excited states. Thereby, the true directionality of the excitation diffusion is revealed. Excellent agreement with experimental donor and acceptor decays and overall transfer efficiencies is found. Even at low acceptor concentrations (down to 0.1%), efficient energy transfer over distances as large as 25 nm was observed due to rapid energy migration through a series of homo-transfer steps with preference along one direction of the structure.

Fluorination of pi-conjugated organic molecules is a strategy to obtain possible n-type conducting and air-stable materials due to the lowering of the frontier molecular orbitals (MOs) by the high electronegativity of fluorine. Nevertheless, the resulting optical gaps may be widened or narrowed, depending on the molecular backbone and/or the number and position of the fluorine atoms. The authors have performed time-dependent density functional theory calculations to address the subtle influence of fluorine substitution on the absolute MO energies and the subsequent impact on the optical transitions in homologous conjugated oligomers based on thiophene and acene units.

A general algorithm allowing the numerical modeling of the time and space dependence of product formation in spherical reaction volumes is described. The algorithm is described by the complete set of mass balance equations. On the basis of these equations, the effects of the diffusion coefficient, reaction rate, bead size, reagent excess, and packing density of the resin beads on the overall reaction rates are determined for second-order reactions. Experimental data of reaction progress are employed to calculate reaction rates and diffusion coefficients in polymer-supported reactions. In addition, the conditions for shell-like product formation are determined, and various strategies for the radial patterning of resin beads are compared. The effect of diffusion on polymer-supported enzyme-catalyzed reactions of the Michaelis-Menten type is treated, as well. Finally, the effects of typical nonideal solid-phase phenomena, namely, the inhomogeneity of rate constants and the concentration dependence of diffusion coefficients, on overall rates are discussed.

The intermolecular arrangement in the solid state and the consequences on the optical and photophysical properties are studied on different derivatives of oligophenylenevinylenes by UV/VIS absorption and angular-resolved polarized fluorescence spectroscopy. Unsubstituted distyrylbenzene (DSB) organizes in a herringbone manner, with the long axes of the molecules oriented in parallel, but the short axes almost perpendicular to each other. Fluorinated distyrylbenzene (F(12)DSB) as well as the DSB:F(12)DSB cocrystals prefer cofacial pi-stacking in the solid state. For all structures, the consequence of the parallel alignment of the transition moments is a strongly blueshifted H-type absorption spectrum and a low radiative rate constant k(F). Significant differences are observed for the emission spectra: the perpendicular arrangement of the short axes in DSB crystals leads to only very weak intermolecular vibronic coupling. Hence the emission spectrum is well structured, very similar to the one in solution. For F(12)DSB and DSB:F(12)DSB, the cofacial arrangement of the adjacent molecules enables strong intermolecular vibronic coupling of adjacent molecules. Thus, an unstructured and strongly redshifted excimerlike emission spectrum is observed. The differences in the electronic nature of the excited states are highlighted by quantum-chemical calculations, revealing the contribution of interchain excitations to the electronic transitions.

The synthesis, characterization, and various photophysical properties of axially substituted tetrapyrazinotetraazaporphyrinatotitanium(IV) oxide (Pyz(4)TAPTiO) (1), tetrapyrazinotetraazaporphyrinatovanadium(IV) oxide (Pyz(4)TAPVO) (2), tetrapyrazinotetraazaporphyrinatozirconium(IV) dihydroxide [Pyz(4)TAPZr(OH)(2)] (3) are reported. Nonlinear optical (NLO) properties of Pyz(4)TAPs 1-3 have been evaluated at 532 nm with nanosecond pulses for optical limiting (OL). It is found that the introduction of nitrogen atoms in the condensed rings of the tetrapyrrolic macrocycles together with the presence of axial substituents lead to an improvement of the excited-state absorption properties in comparison to phthalocyanines (Pcs). In the linear optical regime Pyz(4)TAPs 1-3 display a blue shift (about 50-60 nm) of the main UV-vis absorption bands with respect to Pcs and exhibit orange-red fluorescence, which can be observed with the eye in the case of 1. Frontier electronic orbitals of a Pyz(4)TAP could be depicted from available experimental data and the results of density functional theory (DFT) calculations. In the solid state, Pyz(4)TAPTiO (1) displays photoconducting properties.

Various end-substituted distyrylbenzenes have been synthesized to serve as guest molecules in inclusion compounds to promote efficient energy transport along one-dimensional channels. Their optical and photophysical properties have been characterized at both experimental and theoretical levels. All molecules display a large transition dipole moment between the ground state and lowest excited state and hence a short radiative lifetime (on the order of 1-2 ns). They also exhibit a large spectral overlap between the emission and absorption spectra, which enables efficient energy transport between molecules arranged in a head-to-tail configuration in nanochannels. Hopping rates on the order of 10(12) s(-1) are calculated at a full quantum-chemical level; this is much larger than the radiative lifetimes and opens the way for energy migration over large distances. Changes in the nature of the terminal substituents are found to modulate the optical properties weakly but to impact significantly the energy transfer rates.

A collection of nine pentamethine indocyanine dyes was synthesized, and the photophysical characteristics relevant to applications in cell biology and single molecule detection were analyzed in detail. Substituents at the aromatic system covering the auxochromic series and substitutions in the polymethine chain were investigated with respect to absorption and emission spectra, fluorescence lifetimes, fluorescence quantum yields, and fluorescence autocorrelations. Substitutions in the polymethine chain increased the nonradiative energy dissipation of the excited singlet state and decreased the fluorescence quantum yield, relative to the unsubstituted compound. For substituents at the aromatic rings the fluorescence quantum yield negatively correlates with the position of the substituents in the auxochromic series -SO(3)(-), -H, -F, -CH(3). Compounds with sulfonic acid groups or halogen atoms attached to the indolenine systems had the highest fluorescence quantum yields. The compound S0387 had nearly 70% of the quantum yield of Cy5 and comparable photostability. The free carboxylic acid of S0387 was attached to peptides in high yield and purity by established procedures of solid-phase synthesis. The dye-labeled peptides did not aggregate or bind to tissue culture cells and proteins unspecifically. The indocyanine dye S0387 is therefore an attractive new fluorophore for in vitro and cell-based detection of receptor ligand interaction at nanomolar concentrations by flow cytometry, fluorescence correlation spectroscopy, and laser scanning microscopy.

Spatially resolved single bead analysis in the micrometer range was employed as a tool for evaluating homogeneity, diffusion, and adsorption in solid-phase supported reactions. Fluorescence microscopy (confocal and non-confocal) as well as IR microscopy were used to detect both the distribution of products and the formation of product gradients in representative reactions. For the first time, the optical slices of whole beads obtained by confocal fluorescence microscopy were compared with the fluorescence images of microtome-sliced beads. The experiments revealed that only physical slices of polystyrene beads deliver realistic representations of the distribution of fluorophores, and confirmed-in contrast to a recent report-the homogeneity of functional site distribution in polystyrene beads. Moreover, the pattern of product formation obtained from an acylation reaction as well as from an alkylation reaction were employed as probes to study the impact of bead size, diffusion, and adsorption on the reaction progress. A simulation of the diffusion process was conducted and compared with the experimental results. Diffusional control was found neither in the case of the alkylation nor in the case of the acylation reaction under investigation. As a consequence, the reaction progress was not a function of the bead sizes as proposed in the literature. Interestingly, in the case of rhodamine acylation with substoichiometric amounts an adsorption-controlled reaction was found. This result highlights the significance of adsorptive effects in solid-phase supported chemistry.

A novel Förster donor-acceptor dye pair for an immunoassay based on resonance energy transfer (RET) is characterized with respect to its photophysical properties. As donor and acceptor, we chose the long-wavelength excitable cyanine dyes Cy5 and Cy5.5, respectively. Due to the perfect spectral overlap, an exceptionally high R(0) value of 68.7 A is obtained in solution. For biochemical applications, antibodies (IgG) are labeled with Cy5, while a tracer for competitive binding is synthesized by labeling bovine serum albumin (BSA) with an analyte derivative and Cy5.5. Binding the dyes to proteins at a low dye/protein ratio increases the fluorescence lifetimes and quantum yields, leading to an enhanced R(0) value of 85.2 A. At higher dye/protein ratios, the formation of nonfluorescent dimeric species causes a decrease in the fluorescence lifetime and quantum yield due to RET from monomeric dyes to dimers within one protein molecule. The Förster distances could be calculated using the dimer absorption spectra to 83.9 and 83.6 A for Cy5 and Cy5.5, respectively. Upon binding of the Cy5-labeled IgG to the tracer, efficient quenching of Cy5 fluorescence is observed. Steady-state and time-resolved measurements reveal that approximately 50% of the quenching results in Förster-type RET, while the residual quenching effect is caused by static quenching processes. The applicability of this dye pair is demonstrated in a homogeneous competitive immunoassay for the pesticide simazine.

Microstructuring of surfaces: Electrochemical polymerization after removal of a photolabile protecting group (nitrobenzyl group) represents a new method for spatially resolved immobilization of ligands or receptors. Thus, the electropolymerization of 3-hydroxyphenylacetyl peptides such as 1 on electrodes can be controlled by light., (© 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)

What causes the shape selectivity of C 30 phases? This question can be answered by combining NMR and fluorescence spectroscopies with HPLC separations at various temperatures. The selectivities depend on the ratio of trans to gauche conformations of the alkyl chains, whose dynamic behavior was characterized with a two-dimensional solid-state NMR spectrum (shown on the right)., (© 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)

The fluorescence quantum yields of vapor-deposited (VD) films of α-oligothiophenes,nT, with ring numbers ofn=3-8 and layer thicknesses ofd=3-50 nm were determined at room temperature andT=77 K and compared to the yields of dilute solutions and small (5T)x clusters. The yields of highly oriented ultrathin films are of the order of ΦF=5*10(-5)-1*10(-4). The yields increase strongly with the layer thickness and also upon cooling, but do not reach the values in dilute solution. The main nonradiative deactivation step S1 → T1 in solution was quantified by(1)O2 production, the yields of which systematically decrease withn from ΦF (3T) to 0.36 (6T), in contrast to the fluorescence yields, which increase from ΦF=0.01 (2T) to 0.40 (6T). In films or clusters the S1 → T1 deactivation step must be a very unimportant side reaction: neither(1)O2 nor any signal of triplet-triplet absorption could be positively identified.