Doped Polymer Research Articles

Highly Elastic Full Hydrocarbon Ultralong RTP Polymers with Visible Light Excitable S0→T1 Population

AbstractHighly elastic ultralong organic room temperature phosphorescence (RTP) polymers are highly desired in wearable optoelectronic fields, but they are hardly realized in rubbers since chain segment motions deactivate triplet excitons. In the current work, it is revealed that polystyrene (PS) can inhibit triplet thermal deactivation of coronene (Cor), and it is the serious oxygen diffusion and quenching that disables RTP emission of Cor/polymers. In view of oxygen barrier function of rubbers, PS−polyisoprene−PS tri‐block elastomers (SIS) are used as Cor's doping matrices. The results show that Cor/SIS sheets show bright and ultralong afterglow with RTP lifetime up to 3.64 s in air after brief 365 nm light excitation. More impressively, Cor/SIS and its red fluorescent dye doped sheets all exhibit ultralong room temperature afterglow under large dynamic elastic deformation. Further, all these sheets exhibit long‐wave blue light excited afterglow despite Cor/SIS having no visible light absorption band, and the unique photoexcitation and emission mechanism is verified. This work not only provides the development strategy of the latest elastic RTP materials, but also will evoke a fresh understanding on organic doped RTP polymers.

Effective Model Reduction Scheme for the Electronic Structure of Highly Doped Semiconducting Polymers.

Highly doped organic polymers have emerged as prominent candidates within novel technological disciplines, yet the fundamental correlation between structure and charge transport characteristics still remains missing. Toward this objective, an efficient model reduction scheme for highly doped polymer chains is developed considering the paradigmatic case of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS). The reduced model accounts for the chemical and structural details of the conducting polymer chain in addition to the long-range Coulombic interactions between charge carriers (holes) and dopant ions and the Coulombic repulsion between holes residing on the PEDOT chain. The model is shown to reproduce the intrachain hole-density profile of bulk polymer chains within a mean-field description. Furthermore, and critically, the model is adept at determining the energy distribution of doped PEDOT samples that in effect, influences the hole distribution among polymer chains. The hole distribution so obtained broadly upholds the approximation of a homogeneous charge-carrier distribution in doped polymers commonly found in the literature. In addition, it is observed that the spin configuration of the charge carriers dictates the energetics of the doped chains while it is a critical function of the chain length, carrier density, and disorder parameters.

Highly conductive and uniform PEDOT on poly(acrylic acid-vinylbenzyl chloride) functionalized surfaces

This study demonstrates increasing the uniformity and conductivity of poly(3,4-ethylene dioxythiophene) (PEDOT) thin films synthesized by vapor phase polymerization (VPP) through the utilization of a thin interfacial prime layer on the substrate surface. The prime layer, which is a copolymer of acrylic acid (AA) and vinylbenzyl chloride (VBC), was coated on the substrate surface using initiated chemical vapor deposition (iCVD) method. FTIR and XPS were used to analyze the structure of as-deposited films. The use of P(AA-VBC) copolymer as a prime layer allowed uniform and complete coverage of the oxidant solution on the substrate surface due to the hydrophilic nature of the AA constituent. During the VPP, the existence of the chlorine ions originating from the VBC constituent allowed in-situ doping of the as-deposited polymer, which contributes to the increased uniformity and the conductivity. The experimental studies were carried out to show the increase in uniformity, conductivity and adherence of the as-deposited PEDOT film in the presence of the prime layer. There was nearly a 4-fold increase in the conductivity of as-deposited PEDOT in the presence of the prime layer, with measured conductivity uniformity as high as 96% over a 5×5 cm2 glass surface.

Near-Infrared Room-Temperature Phosphorescence from Monocyclic Luminophores.

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room-temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron-withdrawing groups were attached to the 4H-pyran-4-thione core to further lower the excited state energies. The resulting mini-phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near-infrared (NIR) RTP. Having a molar mass of only 162 g·mol-1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm-1 (403 nm). Thanks to the good processability of the polymer film, light-emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.

Near‐Infrared Room‐Temperature Phosphorescence from Monocyclic Luminophores

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room‐temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron‐withdrawing groups were attached to the 4H‐pyran‐4‐thione core to further lower the excited state energies. The resulting mini‐phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near‐infrared (NIR) RTP. Having a molar mass of only 162 g·mol‐1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm‐1 (403 nm). Thanks to the good processability of the polymer film, light‐emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.

Revealing Energy Density in Porous Carbon Supercapacitors Using Hydroquinone Sulfonic Acid as Cathodic and Alizarin Red S as Anodic Redox Electrolytes.

Exploration of innovative strategies aiming to boost energy densities of supercapacitors without sacrificing the power density and long-term stability is of great importance. Herein, highly porous nitrogen-doped carbon spheres (NPCS) are decorated onto the graphite sheets (GSs) through a hydrothermal route, followed by a chemical activation. The capacitive performance of the NPCS is then enhanced by hydroquinone sulfonic acid (HSQA) incorporation in both cathodic electrolyte and electrode materials. Later, NPCS are decorated with polypyrrole (PPY), in which HSQA takes a versatile role as conjugated polymer dopant and cathodic redox additive. The capacitive performance of the negative electrodes is enhanced by incorporating of alizarin red S (ARS) as anodic redox additive. Finally, PPY(HQSA)@NPCS-GS//NPCS-GS asymmetric supercapacitor is assembled and tested in dual redox electrolyte system containing HQSA-cathodic and ARS-anodic electrolytes. This device delivers a remarkable energy density of 60.37 Wh kg-1, which is close or even better than lead acid batteries. Thus, the present work provides a novel pathway to develop high energy supercapacitors using redox active electrolytes for next-generation energy storage applications.

Tetra dansylamides substituted cyclen and cyclam macrocycles as fluorescent sensing probes for metal ions and temperature-responsive materials in dopped polymers

Two novel tetra-dansyl derivatives incorporating cyclen (1,4,7,10-tetraazacyclododecane) and cyclam (1,4,8,11-tetraazacyclotetradecane) macrocycles have been synthesized, thoroughly characterized, and their photophysical properties examined, both in solution and in the solid state. These compounds exhibit fluorescence emission with quantum yields up to 40 %, varying significantly with different solvents. They also display positive solvatofluorochromic behavior, with emissions ranging from green to yellow colours. Kamlet-Taft studies were conducted to better understand solute-solvent interactions. Furthermore, aggregation-induced emission was observed in solutions with high water content, confirmed via dynamic light scattering. Given the intrinsic properties of these compounds, their potential for environmental remediation was explored through metal ion sensing studies. Compounds L1 and L2 demonstrated high sensitivity to Cu2+ and Hg2+ ions, significantly modulating their emission, with L2 capable of detecting and quantifying Hg2+ concentrations as low as 2–3 μM. Additionally, the solid-state emission of these compounds encouraged an investigation into their potential as temperature sensors. Several doped polymer thin films were fabricated, establishing a linear relationship with temperature beyond their melting point. These findings suggest that these tetra-chromophoric compounds hold promise as molecular thermometers.

Impact of PTQ11 polymer doping on the optoelectronic and structural properties of a CH3NH3PbI3 perovskite photovoltaic cell

At present, one of the most swiftly progressing domains in solar photovoltaics is perovskite-based solar cells. Chemical modification of perovskites with foreign atoms represents a potentially fruitful approach to customizing material characteristics with the aim of enhancing the functionality and durability of solar cells. In this study, we first documented the inverted structure of PTQ11 polymer-doped perovskite solar cells composed of CH3NH3PbI3 (MAPbI3) perovskite thin film. The findings indicate that the active layer morphology is enhanced through PTQ11 doping, leading to rapid suppression of photoluminescence and delayed carrier recombination. The XRD and Raman spectral analyses revealed the crystalline, single phase, tetragonal, and highly pure MAPbI3 thin film with the preferred (220) orientation. Energy gaps ranging from 1.596 eV to 1.577 eV and absorption coefficients exceeding 105 cm−1 were characteristics of the doped thin film, which varied with the doping concentration. A transition occurred on the perovskite film’s surface to form smooth, compressed pores measuring 1.63 µm in diameter. This modification potentially enhanced the photovoltaic performance by facilitating charge transport. With an open circuit voltage of 1.11 V, a power conversion efficiency (PCE) of 18.24 %, a short-circuit current density of 22.32 mA/cm2, and a fill factor of 73.65 %, the PTQ11-9 mg/mL sample constituted the solar cell device base. Hence, the findings suggest that the doping of PTQ11 polymer represents a potentially effective approach to improve the performance of perovskite solar cells.

Nanoscale ZnO doping in prosthetic polymers mitigate wear particle-induced inflammation and osteolysis through inhibiting macrophage secretory autophagy

Wear particles produced by joint replacements induce inflammatory responses that lead to periprosthetic osteolysis and aseptic loosening. However, the precise mechanisms driving wear particle-induced osteolysis are not fully understood. Recent evidence suggests that autophagy, a cellular degradation process, plays a significant role in this pathology. This study aimed to clarify the role of autophagy in mediating inflammation and osteolysis triggered by wear particles and to evaluate the therapeutic potential of zinc oxide nanoparticles (ZnO NPs).We incorporated ZnO into the prosthetic material itself, ensuring that the wear particles inherently carried ZnO, providing a targeted and sustained intervention. Our findings reveal that polymer wear particles induce excessive autophagic activity, which is closely associated with increased inflammation and osteolysis. We identified secretory autophagy as a key mechanism for IL-1β secretion, exacerbating osteolysis. Both in vitro and in vivo experiments demonstrated that ZnO-doped particles significantly inhibit autophagic overactivation, thereby reducing inflammation and osteolysis.In summary, this study establishes secretory autophagy as a critical mechanism in wear particle-induced osteolysis and highlights the potential of ZnO-doped prosthetic polymers for targeted, sustained mitigation of periprosthetic osteolysis.

Hierarchical Dual‐Mode Efficient Tunable Afterglow via J‐Aggregates in Single‐Phosphor‐Doped Polymer

AbstractThe development of polymer‐based persistent luminescence materials with color‐tunable organic afterglow and multiple responses is highly desirable for applications in anti‐counterfeiting, flexible displays, and data‐storage. However, achieving efficient persistent luminescence from a single‐phosphor system with multiple responses remains a challenging task. Herein, by doping 9H‐pyrido[3,4‐b]indole (PI2) into an amorphous polyacrylamide matrix, a hierarchical dual‐mode emission system is developed, which exhibits color‐tunable afterglow due to excitation‐, temperature‐, and humidity‐dependence. Notably, the coexistence of the isolated state and J‐aggregate state of the guest molecule not only provides an excitation‐dependent afterglow color, but also leads to a hierarchical temperature‐dependent afterglow color resulting from different thermally activated delayed fluorescence (TADF) and ultralong organic phosphorescence (UOP) behaviors of the isolated and aggregated states. The complex responsiveness based on the hierarchical dual‐mode emission can serve for security features through inkjet printing and ink‐writing. These findings may provide further insight into the regulated persistent luminescence by isolated and aggregated phosphors in doped polymer systems and expand the scope of stimuli‐responsive organic afterglow materials for broader applications.

Hierarchical Dual-Mode Efficient Tunable Afterglow via J-Aggregates in Single-Phosphor-Doped Polymer.

The development of polymer-based persistent luminescence materials with color-tunable organic afterglow and multiple responses is highly desirable for applications in anti-counterfeiting, flexible displays, and data-storage. However, achieving efficient persistent luminescence from a single-phosphor system with multiple responses remains a challenging task. Herein, by doping 9H-pyrido[3,4-b]indole (PI2) into an amorphous polyacrylamide matrix, a hierarchical dual-mode emission system is developed, which exhibits color-tunable afterglow due to excitation-, temperature-, and humidity-dependence. Notably, the coexistence of the isolated state and J-aggregate state of the guest molecule not only provides an excitation-dependent afterglow color, but also leads to a hierarchical temperature-dependent afterglow color resulting from different thermally activated delayed fluorescence (TADF) and ultralong organic phosphorescence (UOP) behaviors of the isolated and aggregated states. The complex responsiveness based on the hierarchical dual-mode emission can serve for security features through inkjet printing and ink-writing. These findings may provide further insight into the regulated persistent luminescence by isolated and aggregated phosphors in doped polymer systems and expand the scope of stimuli-responsive organic afterglow materials for broader applications.

ESR, UV–vis–NIR and FTIR spectroscopic characterization of charge carriers in copper salen polymeric complexes

In this work, we present spectroscopic investigation of charge carriers in copper(II) salen-type polymeric complexes. The polymers comprising monomeric complexes of copper(II) ion with N2O2 Schiff base ligands are analyzed to understand the influence of the paramagnetic metal center and electron-donating substituents in the ligand on the spectroscopic properties of oxidized polymers. Potential-driven structural changes in the polymeric complexes were monitored using electron spin resonance (ESR), ultraviolet−visible − near infrared (UV−vis − NIR) and Fourier Transform Infrared (FTIR) spectroelectrochemistry. By EPR spectroelectrochemistry, we gained insight into the magnetic properties of charge carriers formed during the initial and deep oxidation of the polymers as well as the interactions between the Cu(II)–ligand spins and ligand–ligand ones. By FTIR spectroelectrochemistry, it has been shown that the charge in the low doped polymers is delocalized within the whole repeat unit.

Improved UV-Vis Detector Performance Prepared via the Electrospinning Technique by Doping Polymer Solutions with Iron Oxide

The iron (III) oxide nanoparticles (NPs) were prepared by a solvent-controlled method when preparing the electrospinning solution. Nanofibers (NFs) were prepared from pure PVP and PVP doped with ratios 1 %wt., 2 %wt. and 3 %wt. of Fe2O3 NPs at room temperature by the electrospinning technique. Optical properties like absorbance and the band energy gap ([Formula: see text]g) were studied, and the direct band gap of pure PVP NFs is 4.07 eV and decreases slightly with increasing concentration of Fe2O3 NPs. The PVP NFs with Fe2O3 NPs were used as a UV-Vis light detector with good responsivity and specific detectives at a mixing rate of 3% Fe2O3 NPs, which was 12 A/W and 27.76 ×10[Formula: see text] Jones at wavelength 458.3 nm, and also had the lowest values for the rise-time and fall-time.

Effect of polypyrrole incorporation amounts on the optical and electrical properties of PVA/CMC blended polymer for optoelectronic applications

In the present work, hybrid flexible blended polymers of polypyrrole (PPy)/polyvinyl alcohol (PVA)/carboxymethyl cellulose (CMC); PVA/CMC/x wt % PPy; were constructed as promising blended materials to be used in various optoelectronics applications. X-ray diffraction and scanning electron microscopy techniques were used to investigate the structure and the surface morphology of polymer nanocomposites. The doped blends have better absorption of the three types of ultraviolet (UVA, UVB, and UVC), as well as the visible spectrum. The transmittance values in the visible range dropped from 90 % to 63 % as the PPy concentration reached 0.5 wt%. At x = 0.5, the minimum direct and indirect optical band gap energy values of (4.82, 4.39, 4.23) eV and (3.76, 3.84, 3.62, 2.93) eV, respectively, were obtained. The incorporation of PPy into the PVA/CMC blend led to a regular rise in the refractive index value within the visible range. The blend doped with 0.5 wt % PPy exhibited the highest optical dielectric constant values within the visible range. The enhancement/reduction in the fluorescence intensity depended on the excitation wavelength and the amount of PPy doping in the blended polymers. The effect of voltage, temperature and the amount of PPy doping on the current behavior of the resulting electric current in all blends was explored. The ohmic and nonohmic natures and the charge transport mechanisms of different blends were determined.

Recent advances in enhancing thermoelectric performance of polymeric materials

The inherent low thermal conductivity, low cost, and flexibility of polymeric materials make them potential candidates for thermoelectric applications. Their eco-friendliness and mechanical flexibility are useful for the design of portable and flexible self-powered electronics. However, the heat-to-electrical power conversion efficiency, also known as the figure-of-merit (ZT), of polymer TE materials is low. Research efforts are in progress to enhance the thermoelectric performance of polymers and to find new kinds of polymer composites. Recent research innovations, such as chemical doping of polymers, development of nanocomposites and hybrid composites, and nanostructuring have significantly changed the thermoelectric properties of the polymeric materials. In this article, we summarize the recent developments and achievements in polymer materials for thermoelectric applications.

Potassium Phthalimide Doped with Delta‐Site Structures to Construct Ultra‐Long Cycle Life Aqueous Zn‐Polymer Batteries

AbstractAqueous Zn‐polymer batteries hold great promise for environmentally friendly energy storage systems. However, the poor cycling performance caused by irreversible structural deformation and polymer chain entanglement during the embedding and de‐embedding processes of Zn2+ and H+ ions is one of the key challenges facing their development. Here a new polyaniline cathode doped is developed with potassium phthalimide using a secondary doping approach. This polymeric electrode integrates the conjugated backbone for charge transport with an anionic phthalimide dopant for constructing a triangular‐site structure, as illustrated by the density functional theory calculations. This unique molecular structure is favorable for improving conductivity and structural stability by effectively modulating the localized electron cloud density. The Zn‐polymer battery holds an outstanding capacity retention of 76.1% after 25,000 cycles at a current density of 1 A g−1 with the coulombic efficiency maintained above 99.4%. This secondary doped polymer strategy offers a new host alternative for the ultra‐long cycle life of Zn‐polymer batteries. The molecular design strategy and the insight into the relationship between the structure and performance may provide some guidelines for developing polymer cathodes with high stability.

Simultaneous Thermally Stimulated Delayed Phosphorescence (TSDP) and Thermally Activated Delayed Fluorescence (TADF) in a Two-Coordinated Au(I) Bimetallic Complex Featuring a Tandem Carbene Structure.

A bimetallic, two-coordinated carbene-metal-amine (cMa) Au(I) complex featuring a twisted tandem carbene structure (NHC1-Au-NHC2-Au-carbazolyl) was synthesized. The molecular structure in single crystals revealed a large dihedral angle between the two carbene ligands, while the bridged carbene NHC2 and carbazolyl (Cz) ligands were coplanar. A bluish green thermally stimulated delayed phosphorescence (TSDP) was observed in crystals with an emission lifetime over 70 μs, which can be attributed to the spin allowed diabatic population of a high-lying emissive triplet state from the 3LE characterized low-lying ones. The small rotation energy barrier of Cz along the coordination bond allowed conformers with large dihedral angles between NHC2 and Cz. The ICT characterized S1 state was consequently stabilized to achieve a thermally accessible energy gap to facilitate ISC between triplets and the S1, leading to the thermally activated delayed fluorescence (TADF). Simultaneous TSDP and TADF dual emission can be recorded in its doped polymer film owing to the coexistence of these different conformers.

Suppressed surface aggregation and homogeneous integration of π-Bridged polyelectrolyte for boosting charge transport in conjugated polymer semiconductors

The introduction of extrinsic materials into host materials has been extensively considered for resolving the challenge of intrinsically low charge movement within semiconducting polymers. One of the difficult issues is developing a dopant that can provide a sufficient interfacial area between host and dopant as well as maintain an efficient charge transport pathway without significantly altering the morphological and crystalline properties of semiconducting polymers. Herein, we propose the use of conjugated polyelectrolyte (CPE), a new highly mixable and mutual dopant for achieving enhanced charge mobility in host conjugated polymers. We found that CPE has more homogeneous dispersion in host polymers than non-conjugated polymeric dopants. This results in enhanced charge mobility in the organic field-effect transistor (OFET) based on a novel p-type semiconducting polymer, poly(3-hexylthiophene) (P3HT) (from 0.076 to 0.135 cm2 V−1 s−1). Atomic force microscopy and grazing incident X-ray diffraction measurements were used to confirm the non-destructive behavior of CPE within P3HT. Therefore, it is believed that CPE is promising for use as a homogeneous chemical dopant for polymer semiconductors.

Using Bulky Dodecaborane-Based Dopants to Produce Mobile Charge Carriers in Amorphous Semiconducting Polymers.

Conjugated polymers are a versatile class of electronic materials featured in a variety of next-generation electronic devices. The utility of such polymers is contingent in large part on their electrical conductivity, which depends both on the density of charge carriers (polarons) and on the carrier mobility. Carrier mobility, in turn, is largely controlled by the separation between the polarons and dopant counterions, as counterions can produce Coulombic traps. In previous work, we showed that large dopants based on dodecaborane (DDB) clusters were able to reduce Coulombic binding and thus increase carrier mobility in regioregular (RR) poly(3-hexylthiophene-2,5-diyl) (P3HT). Here, we use a DDB-based dopant to study the effects of polaron-counterion separation in chemically doped regiorandom (RRa) P3HT, which is highly amorphous. X-ray scattering shows that the DDB dopants, despite their large size, can partially order the RRa P3HT during doping and produce a doped polymer crystal structure similar to that of DDB-doped RR P3HT; Alternating Field (AC) Hall measurements also confirm a similar hole mobility. We also show that use of the large DDB dopants successfully reduces Coulombic binding of polarons and counterions in amorphous polymer regions, resulting in a 77% doping efficiency in RRa P3HT films. The DDB dopants are able to produce RRa P3HT films with a 4.92 S/cm conductivity, a value that is ∼200× higher than that achieved with 3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the traditional dopant molecule. These results show that tailoring dopants to produce mobile carriers in both the amorphous and semicrystalline regions of conjugated polymers is an effective strategy for increasing achievable polymer conductivities, particularly in low-cost polymers with random regiochemistry. The results also emphasize the importance of dopant size and shape for producing Coulombically unbound, mobile polarons capable of electrical conduction in less-ordered materials.

Enhanced Efficiency of Silicon Solar Cell by New Salophen Complexes Embedded PMMA as Light Concentrators

The Schiff base N,N-bis(salicylidene)-o-phenylenediamine (salophen) was prepared by the condensation of salicylaldehyde with o-phenylenediamine in ethanol solution. Two new Zn(II) and Ni(II) salophen complexes, were synthesized, fully characterized by infrared (IR), 1H NMR spectroscopic measurements, UV–Vis spectra, photoluminescence (PL), and X-ray diffraction (XRD). The prepared complexes were used as phosphors to fabricate complexes/PMMA slab-based luminescent solar concentrators (LSC). The thermal stability of pure and doped PMMA polymer was examined by differential scanning calorimetry. Various parameters such as the optical energy gap, refractive index, AC and DC conductivity, dielectric constant, dielectric loss, Urbach energy, fluorescence quantum yield, and Stokes shift have been calculated and discussed. Optical absorption is carried out in wavelength region 200–900 nm at room temperature before and after the samples have been exposed to sunlight for up to 8 h. Photodegradation studies showed that the Zn(II) complex/PMMA LSC has the lowest rate of degradation compared with Ni(II) complex/PMMA LSC with the same concentration (0.06% weight). I–V characteristics of the photovoltaic devices with and without collectors were examined. The PV cell coupled with LSC shows an increase in maximum efficiency by about 50% compared to the normal one. This indicates that the proposed technique is very useful for improving the efficiency of solar cells.