Photophysics of Benzoxazole and Dicyano Functionalised Diketopyrrolopyrrole Derivatives: Insights into Ultrafast Processes and the Triplet State.

Diketopyrrolopyrrole (DPP) functionalised with an electron donating unit acts as a donor-acceptor molecules that have shown potential for application in dyes and photovoltaics. These molecules offer broad absorption/emission properties and structure-dependent dynamics. In this study, we used femtosecond pump-probe spectroscopy to investigate the photo-initiated dynamics of thiophene linked DPP derivatives. The thio-DPPs are further functionalised by different electrons withdrawing terminal groups, namely benzoxazole and thiophene dicyanide. The benzoxazole derivative is strongly emissive and directly relaxes directly to the ground state chloroform solution. Thiophene dicyanide derivative exhibits distinct spectral evolution in the first 10 ps, associated with structural and vibronic process. Later, it crosses over to the triplet state with a yield of 20 %. In the solid-state (thin film), we observed a signal that resembles singlet fission. However, upon careful analysis of temperature-dependent steady state absorbance spectra, we conclude that these features are due to laser-induced thermal artifacts. We describe a simplified excited state evolution in the thin film that does not include any additional excited states. These findings have significant implications for the analysis of triplet formation, which plays a major role in the photophysics of many organic materials.

Synapse-Mimicking Memristors Based on 3,6-Di(tpy)-9-Phenylcarbazole Unimer and Its Copolymer with Cobalt(II) Ions.

The title compound, unimer U (tpy stands for 2,2':6',2″-terpyridin-4'-yl end-group), by itself shows the memristor effect with a retention time of 18 h and persistence of 11 h. Its coordination copolymer with Co(II) ions, [CoU]n, exhibits multimodal resistance changes similar to the synaptic responses observed in biological systems. More than 320 cycles of potentiation and depression measured in continuous sequence occurred without observing a significant current change, confirming the operational stability and reproducibility of the device based on the [CoU]n polymer. The synaptic effect of a device with an indium tin oxide (ITO)/[CoU]n/top-electrode (TE) configuration is more pronounced for the device with TE = Au compared to devices with TE = Al or Ga. However, the latter TEs provide a cost-effective approach without any significant compromise in device plasticity. The detected changes in the synaptic weight, about 12% for pair-pulse facilitation and 80% for its depression, together with a millisecond trigger and reading pulses that decay exponentially on the time scale typical of neurosynapses, justify the device's ability to learn and memorize. These properties offer potential applications in neuromorphic computation and brain-inspired synaptic devices.

Tuning of Morphological and Antibacterial Properties of Poly(3,4-ethylenedioxythiophene):Peroxodisulfate by Methyl Violet.

This study demonstrates a one-step synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) in the presence of the methyl violet (MV) dye. The structural properties of PEDOT:peroxodisulfate were studied using Raman and MALDI-TOF spectroscopies. The use of the MV dye in the polymerization process resulted in a change in the typical irregular morphology of PEDOT:peroxodisulfate, leading to the formation of spherical patterns. SEM and TEM analyses revealed that increasing the dye concentration can produce larger spherical aggregates probably due to the hydrophobic and π-π interactions. These larger aggregates hindered the charge transport and reduced the electrical conductivity. Interestingly, at higher dye concentrations (0.05 and 0.075 M), the PEDOT:peroxodisulfate/MV films exhibited significantly improved antibacterial activity against Staphylococcus aureus and Escherichia coli. Furthermore, the PEDOT:peroxodisulfate films with the incorporated MV dye exhibited a well-defined and repeatable redox behavior. The remarkable amalgamation of their optical, electrochemical and antibacterial properties provides the PEDOT:peroxodisulfate/MV materials with an immensely diverse spectrum of applications, including in optical sensors and medical devices.

Formation of spin-polarized current in antiferromagnetic polymer spintronic field-effect transistors.

We have theoretically investigated the feasibility of constructing a spintronic field-effect transistor with the active channel made of a polymer chain with the antiferromagnetic coupling oriented in the source-to-drain direction. We found two different device function regimes controlling the on-chain spin-charge carrier density by tuning the gate voltage. At higher charge carrier densities, the source-drain current linearly increases with decreasing charge carrier densities. In this regime, no polymer spin-polarized current is observed. Upon reaching a critical gate voltage, the current decreases with decreasing charge densities. It is accompanied by the formation of spin-polarized current, generated by an on-chain process, which can be related to spin-charge spatial distribution symmetry breaking caused either by an application of the source-to-drain voltage (higher spin polarization near the drain), or the breakdown of the Peierls dimerization near chain ends. Numerical simulation of the transistor characteristics suggests that the design of a polymer spintronic field-effect transistor is in principle feasible.

Synthesis and Impedance Spectroscopy of Poly(p-phenylenediamine)/Montmorillonite Composites.

Poly(p-phenylenediamine)/montmorillonite (PPDA/MMT) composites were prepared by the oxidative polymerization of monomers intercalated within the MMT gallery, using ammonium peroxydisulfate as an oxidant. The intercalation process was evidenced by X-ray powder diffraction. The FT-IR and Raman spectroscopies revealed that, depending on the initial ratio between monomers and MMT in the polymerization mixture, the polymer or mainly oligomers are created during polymerization. The DC conductivity of composites was found to be higher than the conductivity of pristine polymer, reaching the highest value of 10-6 S cm-1 for the optimal MMT amount used during polymerization. Impedance spectroscopy was performed over wide frequency and temperature ranges to study the charge transport mechanism. The data analyzed in the framework of conductivity formalism suggest different conduction mechanisms for high and low temperature regions.

Inverse heavy-atom effect in near infrared photoluminescent gold nanoclusters.

Fluorophores functionalized with heavy elements show enhanced intersystem crossing due to increased spin-orbit coupling, which in turn shortens the fluorescence decay lifetime (τPL). This phenomenon is known as the heavy-atom effect (HAE). Here, we report the observation of increased τPL upon functionalisation of near-infrared photoluminescent gold nanoclusters with iodine. The heavy atom-mediated increase in τPL is in striking contrast with the HAE and referred to as inverse HAE. Femtosecond and nanosecond transient absorption spectroscopy revealed overcompensation of a slight decrease in lifetime of the transition associated with the Au core (ps) by a large increase in the long-lived triplet state lifetime associated with the Au shell, which contributed to the observed inverse HAE. This unique observation of inverse HAE in gold nanoclusters provides the means to enhance the triplet excited state lifetime.

Correction: Inverse heavy-atom effect in near infrared photoluminescent gold nanoclusters.

Correction for 'Inverse heavy-atom effect in near infrared photoluminescent gold nanoclusters' by Goutam Pramanik et al., Nanoscale, 2021, DOI: 10.1039/d1nr02440j.

Organic Nanocrystal Fabrication Using the Process of Resonant Second-Harmonic Generation of Light.

Laser ablation with the use of ultra-short laser pulses is a widely used technique for the fabrication of nanoparticles of metals, inorganic and hybrid materials. However, fabrication of fragile organic nanocrystals via laser ablation is rarely used due to easy photodegradation of molecules. The method employing laser irradiation of the target material is beneficial as no other chemicals are used in the production of nanoparticles, except for a given material and a solvent. In this work, we test the concept of formation of nonlinear optical (NLO) organic nanocrystals dispersion in water by irradiation of the microcrystals of the NLO material with nonabsorbed infrared nanosecond light pulses. These pulses, due to a nonlinear optical process active in a noncentrosymmetric organic crystal, such as those studied in this work, DCNP dye (3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole), produce nanosecond pulses of second-harmonic (SH) light. Due to doubling of photon energy, they are reabsorbed in the volume of DCNP microcrystals and thermal shocks fracture them into nanometer size crystals. To the best of our knowledge, such process and its interpretation have not been described yet in the literature.

Iron (II) Metallo-Supramolecular Polymers Based on Thieno[3,2-b]thiophene for Electrochromic Applications.

Four new bis(tpy) unimers with different linkers between the thieno[3,2-b]thiophene-2,5-diyl central unit and terpyridine-4'-yl (tpy) end-groups: no linker (Tt), ethynediyl (TtE), 1,4-phenylene (TtPh) and 2,2'-bithophene-5,5'-diyl (TtB) are prepared, characterized, and assembled with Fe2+ ions to metallo-supramolecular polymers (Fe-MSPs). The Fe-MSP films prepared by spin-casting on Indium Tin Oxide (ITO) glass are characterized by atomic force microscope (AFM) microscopy, cyclic voltammetry, and UV/vis spectroscopy and studied for their electrochromism and effect of the unimer structure on their electrochromic performance. Of the studied MSPs, Fe-Tt shows the highest optical contrast as well as coloration efficiency (CE = 641 cm2 C-1) and the fastest optical response. This makes it an excellent candidate for possible use in electrochromic devices.

Kinetics of the Photoexcited States in Thin Films of Metallo-Supramolecular Polymers With Ditopic Thiophene-Bridged Terpyridine Ligands.

Managing the excited-state decay by a supramolecular structure is a crucial issue for organic photovoltaics. We show that in thin films of metallo-supramolecular polymers made of bis(terpyridine-4'-yl)terthiophenes and Z n 2 + coupling ions, the photoexcited states generated by ultrashort laser pulses at the wavelength of 440 nm decay by the bi-molecular annihilation predominantly controlled by the Förster transfer between singlet states. During this bi-molecular annihilation of singlet states, intermediate hot triplet pairs are formed, which subsequently dissociate into long-living diffusing triplet states. It explains a significant shortening of the triplet state rise time with increasing pump fluence. The diffusion coefficient of triplets showed power-law time dependence, with its exponent proportional to the pump fluence, decreasing thus the diffusivity of triplets.

Singlet Fission in Thin Solid Films of Bis(thienyl)diketopyrrolopyrroles.

The singlet fission (SF) process discovered in bis(thienyl)diketopyrrolopyrroles (TDPPs) can boost their potential for photovoltaics (PV). The crystal structures of TDPP analogs carrying n-hexyl, n-butyl, or 2-(adamant-1-yl)ethyl substituents are similar, but contain increasingly slipped stacked neighbor molecules. The observed SF rate constants, kSF , (7±4), (9±3) and (5.6±1.9) ns-1 for thin films of the three compounds, respectively, are roughly equal, but the triplet quantum yields vary strongly: (120±40), (160±40) and (70±16), respectively. The recent molecular pair model reproduces the near equality of all three kSF at the crystal geometries and identifies all possible pair arrangements in which SF is predicted to be faster, by up to two orders of magnitude. However, it is also clear that the presently non-existent ability to predict the rates of processes competing with SF is pivotal for providing a guide for efforts to optimize the materials for PV.

The biocompatibility of polyaniline and polypyrrole 2: Doping with organic phosphonates.

Conducting polymers (CP) can be used as pH- and/or electro-responsive components in various bioapplications, for example, in 4D smart scaffolds. The ability of CP to maintain conductivity under physiological conditions is, therefore, their crucial property. Unfortunately, the conductivity of the CP rapidly decreases in physiological environment, as their conducting salts convert to non-conducting bases. One of the promising solutions how to cope with this shortcoming is the use of alternative "doping" process that is not based on the protonation of CP with acids but on interactions relying in acidic hydrogen bonding. Therefore, the phosphonates (dimethyl phosphonate, diethyl phosphonate, dibutyl phosphonate, or diphenyl phosphonate) were used to re-dope two most common representatives of CP, polyaniline (PANI) and polypyrrole (PPy) bases. As a result, PANI doped with organic phosphonates proved to have significantly better stability of conductivity under different pH. It has also been shown that cytotoxicity of studied materials determined on embryonic stem cells and their embryotoxicity, determined as the impact on cardiomyogenesis and erythropoiesis, depend both on the polymer and phosphonate types used. With the exception of PANI doped with dibutyl phosphonate, all PPy-based phosphonates showed better biocompatibility than the phosphonates based on PANI.

Impact of Hydrogen Bonds Limited Dipolar Disorder in High-k Polymer Gate Dielectric on Charge Carrier Transport in OFET.

The paper contributes to the characterization and understanding the mutual interactions of the polar polymer gate dielectric and organic semiconductor in organic field effect transistors (OFETs). It has been shown on the example of cyanoethylated polyvinylalcohol (CEPVA), the high-k dielectric containing strong polar side groups, that the conditions during dielectric layer solidification can significantly affect the charge transport in the semiconductor layer. In contrast to the previous literature we attributed the reduced mobility to the broader distribution of the semiconductor density of states (DOS) due to a significant dipolar disorder in the dielectric layer. The combination of infrared (IR), solid-state nuclear magnetic resonance (NMR) and broadband dielectric (BDS) spectroscopy confirmed the presence of a rigid hydrogen bonds network in the CEPVA polymer. The formation of such network limits the dipolar disorder in the dielectric layer and leads to a significantly narrowed distribution of the density of states (DOS) and, hence, to the higher charge carrier mobility in the OFET active channel made of 6,13-bis(triisopropylsilylethynyl)pentacene. The low temperature drying process of CEPVA dielectric results in the decreased energy disorder of transport states in the adjacent semiconductor layer, which is then similar as in OFETs equipped with the much less polar poly(4-vinylphenol) (PVP). Breaking hydrogen bonds at temperatures around 50 °C results in the gradual disintegration of the stabilizing network and deterioration of the charge transport due to a broader distribution of DOS.

Gate voltage impact on charge mobility in end-on stacked conjugated oligomers.

We present a model of the charge transport in thin film organic field-effect transistors with the active channel made of linear conjugated chains stacked on the substrate with end-on-orientation. The transport was simulated in a box consisting of 25 polymer chains, in which the delocalized quantum orbital eigenstates of the on-chain hole distribution were calculated. The inter-chain charge transfer was solved semi-classically. The full self-consistent distribution of charge density and electric field was determined for various applied gate and source-drain voltages. We found that the dependence of charge mobility on gate voltage is not monotonic: it first increases with increasing gate voltage for a limited interval of the latter, otherwise it decreases with the gate voltage. Next, we found formation of the second resonant peak for higher gate voltages. The mobility dependence on the gate voltage confirmed that the current flowing through the active semiconductor layer should be described not only as the hole transfer between adjacent repeat units of the neighbouring chains, but also as the transfer of coherences among on-chain repeat units. The presented model can also give a new insight into the charge transport in organic field-effect transistors with a novel vertical architecture.

Plasmonic Screening Effect of Gold Nanoparticles Array on Light Absorption in Poly(3-hexyl)Thiophene Thin Film.

The localized surface plasmon (LSP) photophysical phenomenon occurring in metal nanostructures is often presented as a way to effectively couple light into sub-wavelength-scale photovoltaic devices, which would otherwise suffer from a weak light absorption. The simultaneous complementary effect of localized optical field depletion receives far less attention. We studied a system consisting of a planar gold nanoparticles array (AuNP) deposited at the surface of a semiconducting polymer thin film (P3HT). By comparing the UV-vis spectra of P3HT with and without the AuNP array, we have estimated that the AuNPs screen the optical absorption in the interfacial layer of about 3.8 nm effective thickness due the near-field depletion effect. It suggests that the AuNP array may be used to practically "hide" a thin semiconductor layer, e.g., in order to tune the perceived color of the photovoltaic cell embedded in architecture, or in wearable devices.

On the methodology of the determination of charge concentration dependent mobility from organic field-effect transistor characteristics.

We developed a new methodology for determining charge concentration dependent mobility from organic field-effect transistor (OFET) characteristics, applicable for semiconducting polymers with structural and energy disorder. We show that basic formulae recommended by the "IEEE Standard for Test Methods for the Characterization of Organic Transistors and Materials" for the determination of the field-effect mobility as obtained from the slope ISD1/2vs. VSG (in the saturation regime) or from the transconductance dISD/dVSG (in the linear regime) are not suitable for materials with concentration dependent charge carrier mobility. We propose alternative expressions, which can be directly analytically derived from the drift-diffusion equation with the mobility explicitly dependent on the charge concentration. This methodology for mobility determination was used for analysis of the experimental data obtained for a poly(3-hexylthiophene)-based OFET with the bottom gate-bottom SD electrode configuration.

Phonons spreading from laser-heated gold nanoparticle array accelerate diffusion of excitons in an underlying polythiophene thin film.

Localized surface plasmon (LSP) photophysical phenomena occurring in metal nanostructures are often presented as a method to effectively couple light into photovoltaic devices of sub-wavelength-scale thickness. However, the excitation of LSP is also associated with rapid energy dissipation leading to local heating, which affects the excitation energy pathway. We studied a system consisting of a planar gold nanoparticle (AuNP) array deposited at the surface of a semiconducting polymer thin film (P3HT). We observed heat transfer from laser pulse excited AuNPs into the P3HT, which was evidenced as a long-living thermochromic effect on transient optical absorption. By modeling of the ultrafast kinetics of exciton population evolution, we determined that their decay was caused by their mutual annihilation. The decay rate was controlled by a phonon-assisted one-dimensional diffusion mechanism with a diffusion constant of 2.2 nm2 ps-1. The transferred heat resulted in an increase of the diffusion constant by a factor of almost 2, compared to the control system of P3HT without AuNPs. These results are of practical use for the design of plasmon-enhanced optoelectronic devices.

Modelling of the charge carrier mobility in disordered linear polymer materials.

We introduced a molecular-scale description of disordered on-chain charge carrier states into a theoretical model of the charge carrier transport in polymer semiconductors. The presented model combines the quantum mechanical approach with a semi-classical solution of the inter-chain charge hopping. Our model takes into account the significant local anisotropy of the charge carrier mobility present in linear conjugated polymers. Contrary to the models based on the effective medium approximation, our approach allowed avoiding artefacts in the calculated concentration dependence of the mobility originated in its problematic configurational averaging. Monte Carlo numerical calculations show that, depending on the degree of the energetic and structural disorder, the charge carrier mobility increases significantly with increasing charge concentration due to trap filling. At high charge carrier concentrations, the effect of the energetic disorder disappears and the mobility decreases slightly due to the lower density of unoccupied states available for the hopping transport. It could explain the experimentally observed mobility degradation in organic field-effect transistors at high gate voltage.

Morphology and Kinetics of Aggregation of Silver Nanoparticles Induced with Regioregular Cationic Polythiophene.

The aggregation kinetics of negatively charged borate-stabilized silver nanoparticles (NPs) induced by the cationic regioregular polythiophene polyelectrolyte poly{3-[6-(1-methylimidazolium-3-yl)hexyl]thiophene-2,5-diyl bromide} (PMHT-Br) and the morphology of formed aggregates have been investigated via ultraviolet-visible light (UV-vis) spectroscopy, transmission electron microscopy (TEM), zeta (ζ) potential measurements, dynamic light scattering (DLS), and time-resolved small-angle X-ray scattering (SAXS). Two or three populations of NPs are formed within milliseconds upon mixing the components, which differ in the mean size, extent of polymer coating, and time stability. These characteristics are primarily controlled by the PMHT-Br to Ag-NPs ratio. Population of single NPs of a mean size of ∼5 nm is present in every system and is mostly stable for a long time. At low ratios, the single NPs are most probably almost free of polymer chains and the second population includes slow, but in a limited extent, growing NPs in which single NPs might be interconnected by polymer chains. At the ratios corresponding to the charge balance in the system (ca. zero ζ-potential of NPs), the NPs aggregate, forming a second population that continuously grows in size, and finally undergo sedimentation. At the high ratios, three long-time stable populations of NPs are observed, having mean sizes of ca. 5, 13, and 35 nm; all NPs should be fully coated with PMHT-Br, giving them a positively charged stabilizing shell.

Time-Resolved Transient Optical Absorption Study of Bis(terpyridyl)oligothiophenes and Their Metallo-Supramolecular Polymers with Zn(II) Ion Couplers.

α,ω-Bis(terpyridyl)oligothiophenes spontaneously assemble with Zn(II) ions giving conjugated constitutional dynamic polymers (dynamers) of the metallo-supramolecular class, which potentially might be utilized in optoelectronics. Their photophysical properties, which are of great importance in this field of application, are strongly influenced by the dynamic morphology. It was assessed in this study by using ultrafast pump-probe optical absorption spectroscopy. We identified and characterized relaxation processes running in photoexcited molecules of these oligomers and dynamers and show impacts of disturbed coplanarity of adjacent rings (twisting the thiophene-thiophene and thiophene-terpyridyl bonds by attached hexyl side groups) and Zn(II) ion couplers on these processes. Major effects are seen in the time constants of rotational relaxation, intersystem crossing, and de-excitation lifetimes. The photoexcited states formed on different repeating units within the same dynamer chain do not interact with each other even at very high excitation density. The method is presented that allows determining the equilibrium fraction of unbound oligothiophene species in a dynamer solution, from which otherwise hardly accessible values of the average degree of polymerization of constitutionally dynamic chains in solution can be estimated.