Room temperature, cascadable, all-optical polariton universal gates.

Today, almost all information processing is performed using electronic logic circuits operating at several gigahertz frequency. All-optical logic holds the promise to allow for up to three orders of magnitude higher speed. Whereas essential all-optical transistor functionalities were demonstrated across a range of platforms, utilising them to implement a complete Boolean logic gate set and in particular negation, i.e. switching off an optical signal with another, weaker, optical signal, poses a major challenge. Here, we realize a cascadable NOT gate by introducing the concept of non-ground-state polariton amplification in organic semiconductor microcavities under non-resonant optical excitation. We unravel the importance of vibron-mediated stimulated scattering in room temperature operation of the inverter. Moreover, we extend the concept to a multi-input universal NOR logic gate, where in the presence of any of the input signals non-ground-state amplification supersedes spontaneous ground-state condensation, resulting in a NOR gate with ~1 ps switching time. The realisation of an ultrafast universal logic gate constitutes an essential step for more complex optical circuitry that could boost information processing applications.

Microporous Polymer-Modified Glassy Carbon Electrodes for the Electrochemical Detection of Metronidazole: Experimental and Theoretical Insights.

The persistence and potential toxicity of emergent pollutants pose significant threats to biodiversity and human health, emphasizing the need for sensors capable of detecting these pollutants at extremely low concentrations before treatment. This study focuses on the development of glassy carbon electrodes (GCEs) modified by films of poly-tris(4-(4-(carbazol-9-yl)phenyl)silanol (PTPTCzSiOH), poly-4,4'-Di(carbazol-9-yl)-1,1'-biphenyl (PCBP), and poly-1,3,5-tri(carbazol-9-yl)benzene (PTCB) for the detection of metronidazole (MNZ) in aqueous media. The films were characterized using electrochemical, microscopy, and spectroscopy techniques, including scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Monomers were electropolymerized through cyclic voltammetry and chronoamperometry techniques. Computational methods at the B3LYP/def2-TZVP level were employed to investigate the structural and electrochemical properties of the monomers. The electrochemical detection of MNZ utilized the linear sweep voltammetry technique. Surface characterization through SEM and XPS confirmed the proper electrodeposition of polymer films. Notably, MPN-GCEs exhibited higher detection signals compared to bare GCEs up to 3.6 times in the case of PTPTCzSiOH-GCEs. This theoretical study provides insights into the structural, chemical, and electronic properties of the polymers. The findings suggest that polymer-modified GCEs hold promise as candidates for the development of electrochemical sensors.

Controlling the Spatial Profile and Energy Landscape of Organic Polariton Condensates in Double-Dye Cavities.

The development of high-speed, all-optical polariton logic devices underlies emerging unconventional computing technologies and relies on advancing techniques to reversibly manipulate the spatial extent and energy of polartion condensates. We investigate active spatial control of polariton condensates independent of the polariton, gain-inducing excitation profile. This is achieved by introducing an extra intracavity semiconductor layer, nonresonant to the cavity mode. Partial saturation of the optical absorption in the uncoupled layer enables the ultrafast modulation of the effective refractive index and, through excited-state absorption, the polariton dissipation. Utilizing an intricate interplay of these mechanisms, we demonstrate control over the spatial profile, density, and energy of a polariton condensate at room temperature.

Influence of Backbone Ladderization and Side Chain Variation on the Orientation of Diketopyrrolopyrrole-Based Donor-Acceptor Copolymers.

Ladder polymers with poly(diketopyrrolopyrrole) (DPP) moieties have recently attracted enormous interest for a large variety of opto-electronic applications. Since the rigidity of the backbone increases with ladderization, a strong influence on the self-organization of thin films is expected. We study the molecular orientation of DPP-based ladder polymers in about 50 nm thin films using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS). Exemplarily, for one polymer, the orientation in thicker films is qualitatively investigated by infrared spectroscopy in transmission. Further, this method allows us to rule out the effects of a possible azimuthal ordering, which would affect the analysis of the orientation by PM-IRRAS. For all polymers, the long axis of the polymer backbone is preferentially oriented parallel to the substrate surface, pointing to a high degree of ordering. It is suggested that the choice of the side chains might be a promising way to tune for face-on and edge-on orientations. The exemplarily performed investigation of interface properties on substrates with different work functions suggests that the choice of the side chains has a minor effect on the interfacial electronic interface structure.

Coordination of Tetracyanoquinodimethane-Derivatives with Tris(pentafluorophenyl)borane Provides Stronger p-Dopants with Enhanced Stability.

Strong molecular dopants for organic semiconductors that are stable against diffusion are in demand, enhancing the performance of organic optoelectronic devices. The conventionally used p-dopants based on 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its derivatives "FxTCN(N)Q", such as 2,3,4,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (F6TCNNQ), feature limited oxidation strength, especially for modern polymer semiconductors with high ionization energy (IE). These small molecular dopants also exhibit pronounced diffusion in the polymer hosts. Here, we demonstrate a facile approach to increase the oxidation strength of FxTCN(N)Q by coordination with four tris(pentafluorophenyl)borane (BCF) molecules using a single-step solution mixing process, resulting in bulky dopant complexes "FxTCN(N)Q-4(BCF)". Using a series of polymer semiconductors with IE up to 5.9 eV, we show by optical absorption spectroscopy of solutions and thin films that the efficiency of doping using FxTCN(N)Q-4(BCF) is significantly higher compared to that using FxTCN(N)Q or BCF alone. Electrical transport measurements with the prototypical poly(3-hexylthiophene-2,5-diyl) (P3HT) confirm the higher doping efficiency of F4TCNQ-4(BCF) compared to F4TCNQ. Additionally, the bulkier structure of F4TCNQ-4(BCF) is shown to result in higher stability against drift in P3HT under an applied electric field as compared to F4TCNQ. The simple approach of solution-mixing of readily accessible molecules thus offers access to enhanced molecular p-dopants for the community.

The Influence of the Side Chain Structure on the Photostability of Low Band Gap Polymers.

Side chains play an important role in the photo-oxidation process of low band gap (LBG) polymers. For example, it has been shown that their photostability can be increased by the introduction of aromatic-oxy-alkyl links. We studied the photostability of prototypical LBG polymers with alkyl and oxyalkyl side chains during irradiation with white light (AM 1.5 conditions) in dry air using UV/vis and IR spectroscopy. Though its degradation kinetics were distinctly affected by the presence or absence of oxygen in the structure of the side chains, in particular cases, the stability was more affected by the presence of linear or branched side chains. Moreover, we showed that the exact position of the alkyl/oxyalkyl side chain at the polymer backbone could be crucial. Although minor effects of chemical modifications on the electronic parameters (ionization potential and gap) were observed, the molecular orientation, determined by polarization modulation-infrared reflection-absorption spectroscopy (PMIRRAS), could be affected. The aggregation and crystallinity of these polymers may distinctly affect their stability.

Thin Polymer Films by Oxidative or Reductive Electropolymerization and Their Application in Electrochromic Windows and Thin-Film Sensors.

Electrically conducting and semiconducting polymers represent a special and still very attractive class of functional chromophores, especially due to their unique optical and electronic properties and their broad device application potential. They are potentially suitable as materials for several applications of high future relevance, for example flexible photovoltaic modules, components of displays/screens and batteries, electrochromic windows, or photocatalysts. Therefore, their synthesis and structure elucidation are still intensely investigated. This article will demonstrate the very fruitful interplay of current electropolymerization research and its exploitation for science education issues. Experiments involving the synthesis of conducting polymers and their assembly into functional devices can be used to teach basic chemical and physical principles as well as to motivate students for an innovative and interdisciplinary field of chemistry.

Circularly Polarized Light Probes Excited-State Delocalization in Rectangular Ladder-type Pentaphenyl Helices.

Ladder-type pentaphenyl chromophores have a rigid, planar π-system and show bright fluorescence featuring pronounced vibrational structure. Such moieties are ideal for studying interchromophoric interactions and delocalization of electronic excitations. We report the synthesis of helical polymers with a rigid square structure based on spiro-linked ladder-type pentaphenyl units. The variation of circular dichroism with increasing chain length provides direct evidence for delocalization of electronic excitations over at least 10 monomeric units. The change in the degree of circular polarization of the fluorescence across the vibronic side bands shows that vibrational motion can localize the excitation dynamically to almost one single unit through breakdown of the Born-Oppenheimer approximation. The dynamic conversion between delocalized and localized excited states provides a new paradigm for interpreting circular dichroism in helical polymers such as proteins and polynucleic acids.

Nanostructuring with Surfactants: The Self-Assembly of a New Poly(thiophene-phenylene) Conjugated Polymer Bearing Azacrown Ether Pendant Groups.

We report the synthesis of a new conjugated polymer bearing crown ether moieties, poly[(N(1-aza-[18]crown-6)carbamido)thiophene-2,5-diyl-alt-1,4-phenylene] (BG2). In water, BG2 forms a dispersion with a slightly cloudy appearance. We have studied the effect of adding surfactants, with different polar head groups, on these polymer-polymer aggregates. Special attention is given to the system with the anionic surfactant, sodium dodecyl sulfate (SDS). The combination of photophysical techniques with electrical conductivity, NMR (1H, 13C, and 27Na), DFT calculations, molecular dynamics simulations, and small-angle neutron scattering (SANS) provides a detailed picture on the behavior of the SDS/BG2 system in aqueous solution and in thin films. NMR, electric conductivity, and DFT results suggest that hydrophilic interactions occur between the polar headgroup of the surfactant (OSO3- Na+) and the aza-[18]-crown-6 moiety. DFT calculations confirmed the capability of BG2 to form stable complexes with the Na+ cations, where the cation can be either inside the azacrown cavity or sandwiched between the cavity and the polymer chain, which seem to determine the position of the surfactant hydrocarbon chain and, therefore, be responsible for the disruption of the BG2 aggregates and subsequent increase in the photoluminescence quantum yields. SANS measurements, made with hydrogenated and deuterated SDS in D2O, clearly show how micron-sized aggregates of BG2 are broken down by SDS and then how BG2 becomes preferentially incorporated within joint colloidal particles of BG2 and SDS with increasing [SDS]/[BG2] molar ratio.

Enhancing Electrochemical Transistors Based on Polymer-Wrapped (6,5) Carbon Nanotube Networks with Ethylene Glycol Side Chains.

Organic electrochemical transistors (ECTs) are an important building block for bioelectronics. To promote the required ion transport through the active layer, state-of-the-art semiconducting polymers feature hydrophilic ethylene glycol side chains that increase the volumetric capacitance and transconductance of the devices. Here, we apply this concept to polymer-wrapped single-walled carbon nanotubes (SWCNTs) as a high-mobility semiconducting material. We replace the polyfluorene copolymer (PFO-BPy), which is used for selectively dispersing semiconducting (6,5) SWCNTs and contains octyl side chains, by an equivalent polymer with tetraethylene glycol side chains. Aerosol-jet printed networks of these SWCNTs are applied as the active layer in water-gated ECTs. These show high hole mobilities (3-15 cm2·V-1·s-1), significantly improved volumetric capacitances and larger transconductances. Thin networks of SWCNTs reach (219 ± 16) F·cm-1·V-1·s-1 as the product of mobility and volumetric capacitance. In situ photoluminescence measurements show more efficient quenching of the near-infrared fluorescence for nanotube networks with hydrophilic glycol side chains compared to those with hydrophobic alkyl side chains, thus corroborating more complete charging under bias. Overall, networks of semiconducting SWCNTs with such tailored wrapping polymers provide excellent device performance. Combined with their inherent mechanical flexibility and durability, they constitute a competitive material for bioelectronics.