Interplay between Theory and Photophysical Characterization in Symmetric α-Substituted Thienyl BODIPY Molecule.

4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based molecules have emerged as interesting materials for optoelectronic applications due to the possibility to easily fine-tune their photophysical and optical properties, dominated by two main absorption bands in the visible range. However, no studies have been reported on the nature of these spectral features. By means of ultrafast spectroscopy, we detect intramolecular energy transfer in a spin-coated film of di-thieno-phenyl BODIPY (DTPBDP) dispersed in a polystyrene matrix after pumping the high-energy absorption band. The same effect is not present upon pumping the lowest-energy band, which instead allows the achievement of efficient amplified spontaneous emission. Density functional calculations indicate the different nature of the two main absorption bands, explaining their different photophysical behavior.

Impact of chiral ligands on photophysical and electro-optical properties of ß-diketonate europium complexes in circularly polarized OLEDs.

Luminescent lanthanide complexes exhibiting chiroptical properties are attracting attention for their application in chiral optoelectronics and photonics, thanks to their unique optical properties, allied to intraconfigurational f-f transitions, which are generally electric-dipole-forbidden and can be magnetic dipole-allowed, which in an appropriate environment can lead to high dissymmetry factors and strong luminescence, in the presence of an antenna ligand. However, because luminescence and chiroptical activity are governed by different selection rules, their successful application in commonly used technologies is still an expectation. Recently, we showed that europium complexes bearing ß-diketonates acting as luminescence sensitizers, and chiral bis(oxazolinyl) pyridine derivatives as the chirality inducer, reasonably perform in circularly polarized (CP) organic light-emitting devices (OLEDs). Indeed, europium ß-diketonate complexes are an interesting molecular starting point, given their strong luminescence and their established use in conventional (i.e., nonpolarized) OLEDs. In this context, it is interesting to investigate in detail the impact of the ancillary chiral ligand on complex emission properties and the performances of corresponding CP-OLEDs. Here we show that, by incorporating the chiral compound as emitter in the architecture of solution processed electroluminescent devices, CP emission is retained, and the efficiency of the device is comparable to reference unpolarized OLED. The observed remarkable dissymmetry values strengthen the position of chiral lanthanide-OLEDs as CP-emitting devices.

A Comparative Study of Cellulose Ethers as Thermotropic Materials for Self-Tracking Solar Concentrators.

The continuous growth in energy demand requires researchers to find new solutions to enlarge and diversify the possible ways of exploiting renewable energy sources. Our idea is the development of a solar concentrator based on trapping the luminous radiation with a smart window. This system is able to direct light towards the photovoltaic cells placed on window borders and produce electricity, without any movable part and without changing its transparency. Herein, we report a detailed study of cellulose ethers, a class of materials of natural origin capable of changing their state, from transparent aqueous solution to scattering hydrogel, in response to a temperature change. Cellulose thermotropism can be used to produce a scattering spot in a window filled with the thermotropic fluid to create a new kind of self-tracking solar concentrator. We demonstrate that the properties of the thermotropic fluid can be finely tuned by selecting the cellulose functionalization, the co-dissolved salt, and by regulating their dosage. Lastly, the results of our investigation are tested in a proof-of-concept demonstration of solar concentration achieved by thermotropism-based light trapping.

Asymmetric AZA-BODIPY with Optical Gain in the Near-Infrared Region.

In recent years, there has been a lot of interest in the development of organic compounds emitting in the near-infrared (NIR) region due to their stimulating applications, such as biosensing and light detection and ranging (LiDAR). Moreover, a lot of effort has been devoted to finding organic emitters with optical gain in the NIR region for lasing applications. In this paper, we present the ultrafast spectroscopy of an asymmetric AZA-BODIPY molecule that shows relevant photophysical changes moving from a diluted solution to a concentrated solution and to a spin-coated film. The diluted solution and the spin-coated film show a bleaching band and a stimulated emission band in the visible region, while the very concentrated solution displays a broad (150 nm) and long-living (more than 400 ps) optical gain band in the NIR region, centered at 900 nm. Our results pave the way for a new organic laser system in a near-infrared spectral region.

Organic Functionalized Carbon Nanostructures for Solar Energy Conversion.

This review presents an overview of the use of organic functionalized carbon nanostructures (CNSs) in solar energy conversion schemes. Our attention was focused in particular on the contribution of organic chemistry to the development of new hybrid materials that find application in dye-sensitized solar cells (DSSCs), organic photovoltaics (OPVs), and perovskite solar cells (PSCs), as well as in photocatalytic fuel production, focusing in particular on the most recent literature. The request for new materials able to accompany the green energy transition that are abundant, low-cost, low-toxicity, and made from renewable sources has further increased the interest in CNSs that meet all these requirements. The inclusion of an organic molecule, thanks to both covalent and non-covalent interactions, in a CNS leads to the development of a completely new hybrid material able of combining and improving the properties of both starting materials. In addition to the numerical data, which unequivocally state the positive effect of the new hybrid material, we hope that these examples can inspire further research in the field of photoactive materials from an organic point of view.

Sulfonate-Conjugated Polyelectrolytes as Anode Interfacial Layers in Inverted Organic Solar Cells.

Conjugated polymers with ionic pendant groups (CPEs) are receiving increasing attention as solution-processed interfacial materials for organic solar cells (OSCs). Various anionic CPEs have been successfully used, on top of ITO (Indium Tin Oxide) electrodes, as solution-processed anode interlayers (AILs) for conventional devices with direct geometry. However, the development of CPE AILs for OSC devices with inverted geometry is an important topic that still needs to be addressed. Here, we have designed three anionic CPEs bearing alkyl-potassium-sulfonate side chains. Their functional behavior as anode interlayers has been investigated in P3HT:PC61BM (poly(3-hexylthiophene): [6,6]-phenyl C61 butyric acid methyl ester) devices with an inverted geometry, using a hole collecting silver electrode evaporated on top. Our results reveal that to obtain effective anode modification, the CPEs' conjugated backbone has to be tailored to grant self-doping and to have a good energy-level match with the photoactive layer. Furthermore, the sulfonate moieties not only ensure the solubility in polar orthogonal solvents, induce self-doping via a right choice of the conjugated backbone, but also play a role in the gaining of hole selectivity of the top silver electrode.

BODIPY-Based Molecules, a Platform for Photonic and Solar Cells.

The 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based molecules have emerged as interesting material for optoelectronic applications. The facile structural modification of BODIPY core provides an opportunity to fine-tune its photophysical and optoelectronic properties thanks to the presence of eight reactive sites which allows for the developing of a large number of functionalized derivatives for various applications. This review will focus on BODIPY application as solid-state active material in solar cells and in photonic devices. It has been divided into two sections dedicated to the two different applications. This review provides a concise and precise description of the experimental results, their interpretation as well as the conclusions that can be drawn. The main current research outcomes are summarized to guide the readers towards the full exploitation of the use of this material in optoelectronic applications.

Efficient Solution-Processed Nanoplatelet-Based Light-Emitting Diodes with High Operational Stability in Air.

Colloidal nanoplatelets (NPLs), owing to their efficient and narrow-band luminescence, are considered as promising candidates for solution-processable light-emitting diodes (LEDs) with ultrahigh color purity. To date, however, the record efficiencies of NPL-LEDs are significantly lower than those of more-investigated devices based on spherical nanocrystals. This is particularly true for red-emitting NPL-LEDs, the best-reported external quantum efficiency (EQE) of which is limited to 0.63% (EQE = 5% for green NPL-LEDs). Here, we address this issue by introducing a charge-regulating layer of a polar and polyelectrolytic polymer specifically engineered with complementary trimethylammonium and phosphonate functionalities that provide high solubility in orthogonal polar media with respect to the NPL active layer, compatibility with the metal cathode, and the ability to control electron injection through the formation of a polarized interface under bias. Through this synergic approach, we achieve EQE = 5.73% at 658 nm (color saturation 98%) in completely solution processed LEDs. Remarkably, exposure to air increases the EQE to 8.39%, exceeding the best reports of red NPL-LEDs by over 1 order of magnitude and setting a new global record for quantum-dot LEDs of any color embedding solution-deposited organic interlayers. Considering the emission quantum yield of the NPLs (40 ± 5%), this value corresponds to a near-unity internal quantum efficiency. Notably, our devices show exceptional operational stability for over 5 h of continuous drive in air with no encapsulation, thus confirming the potential of NPLs for efficient, high-stability, saturated LEDs.

Deep Blue Light Amplification from a Novel Triphenylamine Functionalized Fluorene Thin Film.

The development of high performance optically pumped organic lasers operating in the deep blue still remains a big challenge. In this paper, we have investigated the photophysics and the optical gain characteristics of a novel fluorene oligomer functionalized by four triphenylamine (TPA) groups. By ultrafast spectroscopy we found a large gain spectral region from 420 to 500 nm with a maximum gain cross-section of 1.5 × 10-16 cm2 which makes this molecule a good candidate for photonic applications. Amplified Spontaneous Emission measurements (ASE) under 150 fs and 3 ns pump pulses have revealed a narrow emission at 450 nm with a threshold of 5.5 µJcm-2 and 21 µJcm-2 respectively. Our results evidence that this new fluorene molecule is an interesting material for photonic applications, indeed the inclusion of TPA as a lateral substituent leads to a high gain and consequently to a low threshold blue organic ASE.

In Situ Electroluminescence Color Tuning by Thermal Deprotonation Suitable for Thermal Sensors and Anti-fraud Labels.

A novel and versatile approach to tune photoluminescence and electroluminescence by in situ controlled thermal deprotonation is presented. This methodology, based on a single organic π-conjugated material (pyrene derivative), allows the manufacturing of organic light-emitting diode (OLED) prototypes by solution methods with controlled tunable emission ranging from the orange (protonated form of the dye) to the blue (pristine or deprotonated form). While several protonation/deprotonation cycles can be performed on thin films, for the devices only one cycle is possible so that their use as anti-fraud labels can be envisaged. OLEDs exhibit daylight visible brightness of 150 cd m-2 and device lifetime exceeding 30 hours of continuous operation. Thanks to the simplicity of both material design and device fabrication our approach opens new perspectives in the wide field of thermal sensors for customer care or risk perception.

High-Efficiency All-Solution-Processed Light-Emitting Diodes Based on Anisotropic Colloidal Heterostructures with Polar Polymer Injecting Layers.

Colloidal quantum dots (QDs) are emerging as true candidates for light-emitting diodes with ultrasaturated colors. Here, we combine CdSe/CdS dot-in-rod heterostructures and polar/polyelectrolytic conjugated polymers to demonstrate the first example of fully solution-based quantum dot light-emitting diodes (QD-LEDs) incorporating all-organic injection/transport layers with high brightness, very limited roll-off and external quantum efficiency as high as 6.1%, which is 20 times higher than the record QD-LEDs with all-solution-processed organic interlayers and exceeds by over 200% QD-LEDs embedding vacuum-deposited organic molecules.

Near-IR Emitting Iridium(III) Complexes with Heteroaromatic ß-Diketonate Ancillary Ligands for Efficient Solution-Processed OLEDs: Structure-Property Correlations.

Three NIR-emitting neutral Ir(III) complexes [Ir(iqbt)2 (dpm)] (1), [Ir(iqbt)2 (tta)] (2), and [Ir(iqbt)2 (dtdk)] (3) based on the 1-(benzo[b]thiophen-2-yl)-isoquinolinate (iqtb) were synthesized and characterized (dpm=2,2,6,6-tetramethyl-3,5-heptanedionate; tta=2-thienoyltrifluoroacetonate; dtdk=1,3-di(thiophen-2-yl)propane-1,3-dionate). The compounds emit between λ=680 and 850 nm with high luminescence quantum yields (up to 16 %). By combining electrochemistry, photophysical measurements, and computational modelling, the relationship between the structure, energy levels, and properties were investigated. NIR-emitting, solution-processed phosphorescent organic light-emitting devices (PHOLEDs) were fabricated using the complexes. The devices show remarkable external quantum efficiencies (above 3 % with 1) with negligible efficiency roll-off values, exceeding the highest reported values for solution-processible NIR emitters.

Anti-Oxidation Agents to Prevent Dye Degradation in Organic-Based Host-Guest Systems Suitable for Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) have been extensively studied as they offer a practical solution to increase the efficiency of silicon-based photovoltaics (PVs). In this context, the use of natural and organic luminescent materials is desirable in order to obtain sustainable and environmentally friendly devices. Moreover, solution-processable organic host-guest systems based on Foerster Resonant Energy Transfer (FRET) processes offer the possibility to exploit a low-cost technique to obtain an efficient energy downshift from the UV-visible to red or deep red emissions in order to concentrate the radiation in the area of maximum efficiency of the PV device. Nevertheless, organic materials are subjected to photodegradation that reduces their optical properties when exposed to UV light and oxygen. In this work, we incorporated two different antioxidant molecules (i.e., octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Octa) and L-ascorbic acid (L-Asc)) in a three-dye host-guest system and studied the corresponding optical properties after prolonged irradiation times in air. It was found that the presence of the antioxidants, especially L-Asc, slowed the system's photodegradation down whilst at the same time retaining high emission efficiencies and without interfering with the cascade Resonant Energy Transfer processes among the dyes inserted in the nanochannels of the host.

Bacteria as sensors: Real-time NMR analysis of extracellular metabolites detects sub-lethal amounts of bactericidal molecules released from functionalized materials.

BACKGROUND: Cells exposed to stress factors experience time-dependent variations of metabolite concentration, acting as reliable sensors of the effective concentration of drugs in solution. NMR can detect and quantify changes in metabolite concentration, thus providing an indirect estimate of drug concentration. The quantification of bactericidal molecules released from antimicrobial-treated biomedical materials is crucial to determine their biocompatibility and the potential onset of drug resistance. METHODS: Real-time NMR measurements of extracellular metabolites produced by bacteria grown in the presence of known concentrations of an antibacterial molecule (irgasan) are employed to quantify the bactericidal molecule released from antimicrobial-treated biomedical devices. Viability tests assess their activity against E. coli and S. aureus planktonic and sessile cells. AFM and contact angle measurements assisted in the determination of the mechanism of antibacterial action. RESULTS: NMR-derived concentration kinetics of metabolites produced by bacteria grown in contact with functionalized materials allows for indirectly evaluating the effective concentration of toxic substances released from the device, lowering the detection limit to the nanomolar range. NMR, AFM and contact angle measurements support a surface-killing mechanism of action against bacteria. CONCLUSIONS: The NMR based approach provides a reliable tool to estimate bactericidal molecule release from antimicrobial materials. GENERAL SIGNIFICANCE: The novelty of the proposed NMR-based strategy is that it i) exploits bacteria as sensors of the presence of bactericidal molecules in solution; ii) is independent of the chemo-physical properties of the analyte; iii) establishes the detection limit to nanomolar concentrations.

Thiophene based europium ß-diketonate complexes: effect of the ligand structure on the emission quantum yield.

The synthesis and the molecular and photophysical characterization, together with solid state and solution structure analysis, of a series of europium complexes based on ß-diketonate ligands are reported. The Eu(III) complex emission, specifically its photoluminescence quantum yield (PL-QY), can be tuned by changing ligands which finely modifies the environment of the metal ion. Steady-state and time-resolved emission spectroscopy and overall PL-QY measurements are reported and related to geometrical features observed in crystal structures of some selected compounds. Moreover, paramagnetic NMR, based on the analogous complexes with other lanthanides, are use to demonstrate that there is a significant structural reorganization upon dissolution, which justifies the observed differences in the emission properties between solid and solution states. The energy of the triplet levels of the ligands and the occurrence of nonradiative deactivation processes clearly account for the luminescence efficiencies of the complexes in the series.

Hybrid MoS2/PEDOT:PSS transporting layers for interface engineering of nanoplatelet-based light-emitting diodes.

Colloidal semiconductor nanoplatelets (NPLs) are a subgroup of quantum confined materials that have recently emerged as promising active materials for solution processed light-emitting diodes (LEDs) thanks to their peculiar structural and electronic properties as well as their reduced dimensionality. Nowadays, the conventional structure for NPL-based LEDs makes use of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as a hole transporting layer (HTL). This is a well-known conjugated conductive polymer because it leads to high LED efficiency, though it has limited stability in air due to its intrinsic acidity and hygroscopicity. Here, we develop a nanocomposite aqueous ink, obtained by blending commercial PEDOT:PSS with water-based, stable and highly concentrated molybdenum disulfide (MoS2) nanosheets, obtained via liquid phase exfoliation (LPE), which is suitable as a HTL for solution processed NPL-based LEDs. We demonstrate that the MoS2 additive effectively works as a performance booster in unpackaged devices, thereby prolonging the lifetime up to 1000 hours under ambient conditions. Moreover, the addition of MoS2 induces a modification of the anode interface properties, including a change in the work function and a significant enhancement of the permittivity of the HTL.

The role of triphenylamine in the stabilization of highly efficient polyfluorene-based OLEDs: a model oligomers study.

In order to understand the factors responsible for the improved efficiency and stability of organic light-emitting diodes (OLEDs) based on poly(9,9-dioctylfluorene) (PFO) when triphenylamine (TPA) is introduced as lateral fluorene substituent, we synthetize mono-disperse fluorene-thiophene oligomers as model compounds. Their blends with different concentrations of the fluorenone containing oligomer are studied in order to verify if only a reduction of ketonic defect sites or also an impeded energy transfer (ET) towards such sites are responsible for the suppression of the green emission band. We show that the introduction of TPA groups leads specifically both to an antioxidant action and a reduced ET towards residual defect sites, thanks to the environmental micro-encapsulation role played by TPA units surrounding the polymer backbone. As a result, the performances and colour stability of a device fabricated with TPA-substituted PFO (PFTPA) are strongly improved with respect to standard PFO device prepared in the same conditions.

Highly emissive nanostructured thin films of organic host-guests for energy conversion.

All-organic nanostructured host-guest systems, based on dyes inserted in the nanochannels of perhydrotriphenylene (PHTP) and deoxycholic acid (DCA), show enhanced fluorescence properties with quantum yields even higher than those of the dyes in solution, thanks to the high concentration of emissive molecules with controlled spatial and geometrical organization that prevents aggregation quenching. Both host molecules crystallize, growing with the long axis oriented along the direction of the nanochannels where the linear-chain dyes are inserted, to yield crystals emitting well-polarized light. For the DCA-based host-guests, homogeneous thin films suitable for several applications are obtained. Colour emission in such films can be tuned by co-inclusion of two or three dyes due to resonant energy-transfer processes. We show that films obtained by low-cost techniques, such as solution casting and spin-coating, convert UV light into visible light with an efficiency much higher than that of the standard polymeric blends.

A bifunctional conjugated polyelectrolyte for the interfacial engineering of polymer solar cells.

In this work a novel combination of side chain functionalities, alkyl-phosphonate (EP) and alkyl-ammonium bromide (NBr) groups, on a polyfluorene backbone (PF-NBr-EP) was studied as cathode interfacial material (CIM) in polymer-based solar cells. The devices were made with a conventional geometry, with PTB7:PC71 BM as active layer and aluminum as metal electrode. The CIM showed good solubility in ethanol and film forming ability onto the active layer so that its deposition could be finely tuned. The interface engineering imparted by this CIM was assessed and discussed through kelvin probe force microscopy (KPFM), impedance spectroscopy, charge recombination and electron transport characterizations. To discriminate between the interfacial modifications imparted by the interlayer and its solvent, we included in this study a surface ethanol treated device. In the optimized conditions an average power conversion efficiency of 7.24% was obtained, which is about 60% higher when compared to devices made with bare Al and 26% when compared to devices made with a standard calcium/aluminum cathode. Besides performances, some insights about the devices shelf life stability are also presented. A good persistency through aging was found for the cathode interfacial engineering capabilities of PF-NBr-EP.

High-Aspect-Ratio Semiconducting Polymer Pillars for 3D Cell Cultures.

Hybrid interfaces between living cells and nano/microstructured scaffolds have huge application potential in biotechnology, spanning from regenerative medicine and stem cell therapies to localized drug delivery and from biosensing and tissue engineering to neural computing. However, 3D architectures based on semiconducting polymers, endowed with responsivity to visible light, have never been considered. Here, we apply for the first time a push-coating technique to realize high aspect ratio polymeric pillars, based on polythiophene, showing optimal biocompatibility and allowing for the realization of soft, 3D cell cultures of both primary neurons and cell line models. HEK-293 cells cultured on top of polymer pillars display a remarkable change in the cell morphology and a sizable enhancement of the membrane capacitance due to the cell membrane thinning in correspondence to the pillars' top surface, without negatively affecting cell proliferation. Electrophysiology properties and synapse number of primary neurons are also very well preserved. In perspective, high aspect ratio semiconducting polymer pillars may find interesting applications as soft, photoactive elements for cell activity sensing and modulation.