Search Results (20)

Optimizing charge transport in organic semiconductors is crucial for advancing next-generation optoelectronic devices. The performance of organic field-effect transistors (OFETs) is significantly influenced by the alignment of films in the channel direction and the quality of the dielectric surface, which should be uniform, smooth, and free of charge-trapping defects. Our study reports the enhancement of OFET performance using large-area, uniform, and oriented thin films of regioregular poly[3-hexylthiophene] (RR-P3HT), prepared via the Floating Film Transfer Method (FTM) on octadecyltrichlorosilane (OTS) passivated SiO₂ surfaces. SiO₂ surfaces inherently possess dangling bonds that act as charge traps, but these can be effectively passivated through optimized surface treatments. OTS treatment has improved the optical anisotropy of thin films and the surface wettability of SiO₂. Notably, using octadecene as a solvent during OTS passivation, as opposed to toluene, resulted in a significant enhancement of charge carrier transport. Specifically, passivation with OTS-F (10 mM OTS in octadecene at 100 °C for 48 h) led to a >150 times increase in mobility and a reduction in threshold voltage compared to OTS-A (5 mM OTS in toluene for 12 h at room temperature). Under optimal conditions, these FTM-processed RR-P3HT films achieved the best device performance, with a saturated mobility (μ_sat) of 0.18 cm²V⁻¹s⁻¹. Full article

Chemical doping is a well-established technique for increasing the electrical conductivity of polyconjugated polymers, and its effectiveness can be assessed through IR spectroscopy, thanks to the rise of the so-called IRAVs (infrared activated vibrations), which prove the formation of polarons on the polymer chain. While the mechanism of the IRAVs activation has been widely explored in the past, several peculiar features remain unclear. Changes in the Raman spectrum of doped polymers (RaAV, Raman activated vibrations) are widely used as well for monitoring the doping process, but the interpretation is often limited to purely empirical correlations. By means of an experimental campaign on doped regio-regular poly(3-hexylthiophene-2,5-diyl) (P3HT) samples in chloroform solution and on the solid samples cast from the same solutions, this paper presents for the first time a thorough comparative analysis of IRAVs and RaAVs, aiming at a unified description of the structure of doped P3HT. In particular, we will discuss the effect of the doping level on the vibrational features of the polymer and the dopant so that spectroscopic markers can be found to be used in the identification of the presence of ICT (integer charge transfer) complexes in different doping regimes. This study demonstrates that combining IR, Raman, and UV-Vis-NIR spectroscopies provides a powerful, complementary set of tools to diagnose not only the doping level but also the detailed molecular and supramolecular structure of the doped P3HT, useful for the development of structure/properties relationships in the perspective of the optimization of the charge transport performances. Full article

In the present paper the humidity sensing properties of regioregular rr-P3HT (poly-3-hexylthiophene) polymer films is investigated by means of surface acoustic wave (SAW) based sensors implemented on LiNbO₃ (128⁰ Y-X) and ST-quartz piezoelectric substrates. The polymeric layers were deposited along the SAW propagation path by spray coating method and the layers thickness was measured by atomic force microscopy (AFM) technique. The response of the SAW devices to relative humidity (rh) changes in the range ~5–60% has been investigated by measuring the SAW phase and frequency changes induced by the (rh) absorption in the rr-P3HT layer. The SAW sensor implemented onto LiNbO₃ showed improved performance as the thickness of the membrane increases (from 40 to 240 nm): for 240 nm thick polymeric membrane a phase shift of about −1.2 deg and −8.2 deg was measured for the fundamental (~78 MHz operating frequency) and 3rd (~234 MHz) harmonic wave at (rh) = 60%. A thick rr-P3HT film (~600 nm) was deposited onto the quartz-based SAW sensor: the sensor showed a linear frequency shift of ~−20.5 Hz per unit (rh) changes in the ~5–~50% rh range, and a quite fast response (~5 s) even at low humidity level (~5% rh). The LiNbO₃ and quartz-based sensors response was assessed by using a dual delay line system to reduce unwanted common mode signals. The simple and cheap spray coating technology for the rr-P3HT polymer films deposition, complemented with fast low level humidity detection of the tested SAW sensors (much faster than the commercially available Michell SF-52 device), highlight their potential in a low-medium range humidity sensing application. Full article

Conjugated polymers (CPs) offer the potential for sustainable semiconductor devices due to their low cost and inherent molecular self-assembly. Enhanced crystallinity and molecular orientation in thin films of solution-processable CPs have significantly improved organic electronic device performance. In this work, three methods, namely spin coating, dip coating, and unidirectional floating-film transfer method (UFTM), were utilized with their parametric optimization for fabricating RR-P3HT films. These films were then utilized for their characterization via optical and microstructural analysis to elucidate dominant roles of molecular orientation and crystallinity in controlling charge transport in organic field-effect transistors (OFETs). OFETs fabricated by RR-P3HT thin films using spin coating and dip coating displayed field-effect mobility (μ) of 8.0 × 10⁻⁴ cm²V⁻¹s⁻¹ and 1.3 × 10⁻³ cm²V⁻¹s⁻¹, respectively. This two-time enhancement in µ for dip-coated films was attributed to its enhanced crystallinity. Interestingly, UFTM film-based OFETs demonstrated μ of 7.0 × 10⁻² cm²V⁻¹s⁻¹, >100 times increment as compared to its spin-coated counterpart. This superior device performance is attributed to the synergistic influence of higher crystallinity and molecular orientation. Since the crystallinity of dip-coated and UFTM-thin films are similar, ~50 times improved µ of UFTM thin films, this suggests a dominant role of molecular orientation as compared to crystallinity in controlling the charge transport. Full article

Ternary organic solar cells contain a single three-component photoactive layer with a wide absorption window, achieved without the need for multiple stacking. However, adding a third component into a well-known binary blend can influence the energetics, optical window, charge carrier transport, crystalline order and conversion efficiency. In the form of binary blends, the low-bandgap regioregular polymer donor poly(3-hexylthiophene-2,5-diyl), known as P3HT, is combined with the acceptor PC₆₁BM, an inexpensive fullerene derivative. Two different non-fullerene acceptors (ITIC and eh-IDTBR) are added to this binary blend to form ternary blends. A systematic comparison between binary and ternary systems was carried out as a function of the thermal annealing temperature of organic layers (100 °C and 140 °C). The power conversion efficiency (PCE) is improved due to increased fill factor (FF) and open-circuit voltage (V_oc) for thermal-annealed ternary blends at 140 °C. The transport properties of electrons and holes were investigated in binary and ternary blends following a Space-Charge-Limited Current (SCLC) protocol. A favorable balanced hole–electron mobility is obtained through the incorporation of either ITIC or eh-IDTBR. The charge transport behavior is correlated with the bulk heterojunction (BHJ) morphology deduced from atomic force microscopy (AFM), contact water angle (CWA) measurement and 2D grazing-incidence X-ray diffractometry (2D-GIXRD). Full article

Aligned polymer nanofibres are prepared by means of the electrospinning of a chlorobenzene solution containing regioregular poly(3-hexyltiophene-2,5-diyl), P3HT, and poly(ethylene oxide), PEO. The PEO scaffold is easily dissolved with acetonitrile, leaving pure P3HT fibres, which do not show structural modification. Polymer fibres, either with or without the PEO supporting polymer, are effectively doped by exposure to iodine vapours. Doping is monitored following the changes in the doping-induced vibrational bands (IRAVs) observed in the infrared spectra and by means of Raman spectroscopy. Molecular orientation inside the fibres has been assessed by means of IR experiments in polarised light, clearly demonstrating that electrospinning induces the orientation of the polymer chains along the fibre axis as well as of the defects introduced by doping. This work illustrates a case study that contributes to the fundamental knowledge of the vibrational properties of the doping-induced defects—charged polarons—of P3HT. Moreover, it provides experimental protocols for a thorough spectroscopic characterisation of the P3HT nanofibres, and of doped conjugated polymers in general, opening the way for the control of the material structure when the doped polymer is confined in a one-dimensional architecture. Full article

In this work, the electrospinning technique is used to fabricate a polymer-polymer coaxial structure nanofiber from the p-type regioregular polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) and the n-type conjugated ladder polymer poly(benzimidazobenzophenanthroline) (BBL) of orthogonal solvents. Generally, the fabrication of polymeric coaxial nanostructures tends to be troublesome. Using the electrospinning technique, P3HT was successfully used as the core, and the BBL as the shell, thus conceptually forming a p-n junction that is cylindrical in form with diameters in a range from 280 nm to 2.8 µm. The UV–VIS of P3HT/PS blend solution showed no evidence of separation or precipitation, while the combined solutions of P3HT/PS and BBL were heterogeneous. TEM images show a well-formed coaxial structure that is normally not expected due to rapid reaction and solidification when mixed in vials in response to orthogonal solubility. For this reason, extruding it by using electrostatic forces promoted a quick elongation of the polymers while forming a concise interface. Single nanofiber electrical characterization demonstrated the conductivity of the coaxial surface of ~1.4 × 10⁻⁴ S/m. Furthermore, electrospinning has proven to be a viable method for the fabrication of pure semiconducting coaxial nanofibers that can lead to the desired fabrication of fiber-based electronic devices. Full article

Polymeric thin films offer a wide range of exciting properties and applications, with several advantages compared to inorganic counterparts. The thermal conductivity of such thin films ranges typically between 0.1–1 W m${}^{-1}$ K${}^{-1}$. This low thermal conductivity can cause problems with heat dissipation in various applications. Detailed knowledge about thermal transport in polymeric thin films is desired to overcome these shortcomings, especially in light of the multitude of possible microstructures for semi-crystalline thin films. Therefore, poly(3-hexylthiophene-2,5-diyl) (P3HT) is chosen as a model system to analyze the microstructure and optoelectronic properties using X-ray scattering and absorption spectra along with the thermal transport properties using the photoacoustic technique. This combination of analysis methods allows for determining the optoelectronic and thermal transport properties on the same specimen, supplemented by structural information. The effect of different molecular weights and solvents during film preparation is systematically examined. A variation of the optoelectronic properties, mainly regarding molecular weight, is apparent, while no direct influence of the solvent during preparation is discernible. In contrast, the thermal conductivities of all films examined fall within a similar range. Therefore, the microstructural properties in the ordered regions do not significantly affect the resulting thermal properties in the sample space investigated in this work. We conclude that it is mainly the amorphous regions that determine the thermal transport properties, as these represent a bottleneck for thermal transport. Full article

In this study, electron-donating semicrystalline generation 1 poly(propylene thiophenoimine)-co-poly(3-hexylthiophene) star copolymer, G1PPT-co-P3HT was chemically prepared for the first time. Copolymerization was achieved with high molecular weight via facile green oxidative reaction. ¹H NMR analyses of the star copolymer demonstrated the presence of 84% regioregular (rr) head-to-tail (HT) P3HT, which accounts for the molecular ordering in some grain regions in the macromolecule’s morphology, as revealed by the high-resolution scanning electron microscopy (HRSEM) and Selected Area Electron Diffraction (SAED) images, and X-ray diffraction spectroscopy (XRD) measurements. The star copolymer also exhibited good absorption properties in the ultraviolet-visible (UV-Vis) and the near infrared (NIR) spectral regions, which give rise to an optical energy bandgap value as low as 1.43 eV. A HOMO energy level at −5.53 eV, which is below the air-oxidation threshold, was obtained by cyclic voltammetry (CV). Electrochemical impedance spectroscopy (EIS) ascertained the semiconducting properties of the macromolecule, which is characterized by a charge transfer resistance, R_ct, value of 3.57 kΩ and a Bode plot-phase angle value of 75°. The combination of the EIS properties of G1PPT-co-P3HT and its highly electron-donating capability in bulk heterojunction (BHJ) active layer containing a perylene derivative, as demonstrated by photoluminescence quenching coupled to the observed Förster Resonance charge transfer, suggests its suitability as an electron-donor material for optoelectronic and photovoltaic devices. Full article

Non-covalent functionalisation of the carbon nanotube (CNT) sidewall through polymer wrapping is the key strategy for improving well-dispersed CNTs without persistent alteration of their electronic properties. In this work, the effect of reaction time on regioregular poly (3-hexylthiophene-2,5-diyl) (P3HT)-wrapped hydroxylated multi-walled CNT (MWCNT-OH) nanocomposites was investigated. Five different reaction times (24, 48, 72, 96, and 120 h) were conducted at room temperature in order to clearly determine the factors that influenced the quality of wrapped MWCNT-OH. Morphological analysis using Field Emission Scanning Electron Microscopic (FESEM) and High-Resolution Transmission Electron Microscope (HRTEM) analysis showed that P3HT successfully wrapped the MWCNT-OH sidewall, evidenced by the changes in the mean diameter size of the nanocomposites. Results obtained from Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS) as well as Thermogravimetric Analysis (TGA) showed a significant effect of the wrapped polymer on the CNT sidewall as the reaction time increased. Overall, the method used during the preparation of P3HT-wrapped MWCNT-OH and the presented results significantly provided a bottom-up approach to determine the effect of different reaction times on polymer wrapping to further expand this material for novel applications, especially chemical sensors. Full article

Phase diagrams of n-type low bandgap poly{(N,N′-bis(2-octyldodecyl)naphthalene -1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-5,5′,-(2,2′-bithiophene)} (P(NDI2OD-T2)) solutions and blends were constructed. To this end, we employed the Flory–Huggins (FH) lattice theory for qualitatively understanding the phase behavior of P(NDI2OD-T2) solutions as a function of solvent, chlorobenzene, chloroform, and p-xylene. Herein, the polymer–solvent interaction parameter (χ) was obtained from a water contact angle measurement, leading to the solubility parameter. The phase behavior of these P(NDI2OD-T2) solutions showed both liquid–liquid (L–L) and liquid–solid (L–S) phase transitions. However, depending on the solvent, the relative position of the liquid–liquid phase equilibria (LLE) and solid–liquid phase equilibria (SLE) (i.e., two-phase co-existence curves) could be changed drastically, i.e., LLE > SLE, LLE ≈ SLE, and SLE > LLE. Finally, we studied the phase behavior of the polymer–polymer mixture composed of P(NDI2OD-T2) and regioregular poly(3-hexylthiophene-2,5-dyil) (r-reg P3HT), in which the melting transition curve was compared with the theory of melting point depression combined with the FH model. The FH theory describes excellently the melting temperature of the r-reg P3HT/P(NDI2OD-T2) mixture when the entropic contribution to the polymer–polymer interaction parameter (χ = 116.8 K/T − 0.185, dimensionless) was properly accounted for, indicating an increase of entropy by forming a new contact between two different polymer segments. Understanding the phase behavior of the polymer solutions and blends affecting morphologies plays an integral role towards developing polymer optoelectronic devices. Full article

The initial charge separation process of conjugated polymers is one of the key factors for understanding their conductivity. The structure of photogenerated transients in conjugated polymers can be observed by resonance Raman spectroscopy in the near-IR region because they exhibit characteristic low-energy transitions. Here, we investigate the structure and dynamics of photogenerated transients in a regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) blend film, as well as in a pristine P3HT film, using femtosecond time-resolved resonance inverse Raman spectroscopy in the near-IR region. The transient inverse Raman spectrum of the pristine P3HT film at 50 ps suggests coexistence of neutral and charged excitations, whereas that of the P3HT:PCBM blend film at 50 ps suggests formation of positive polarons with a different structure from those in an FeCl₃-doped P3HT film. Time-resolved near-IR inverse Raman spectra of the blend film clearly show the absence of charge separation between P3HT and PCBM within the instrument response time of our spectrometer, while they indicate two independent pathways of the polaron formation with time constants of 0.3 and 10 ps. Full article

A type of graft copolymer based on polysiloxane and regioregular poly(3-hexylthiophene) (P3HT) has been synthesised and its properties have been studied alongside those of its parent conjugated polymer—regioregular P3HT. Electrochemical analysis has revealed more significant changes in conformation of the copolymer film than was observed for P3HT. UV-Vis-NIR spectroelectrochemical investigation provided evidence of improved doping reversibility of the copolymer, despite its marginally increased band gap, as also confirmed by electroconductometric analysis. Evidence has been shown, indicating that polaron mobilities in both P3HT and the copolymer are higher than those of bipolaronic charge carriers, even though both systems exhibit standard doping/dedoping patterns. The grafted copolymer was tested in bulk heterojunction solar cells. Preliminary studies show a great potential of these polymers for application in photovoltaics. Power conversion efficiency of up to 2.46% was achieved despite the dilution of the P3HT chains in the copolymer. Full article

A new type of polysiloxane copolymers, with conjugated–regioregular poly(3-hexylthiophene) (P3HT) and non-conjugated-poly(ethylene glycol) (PEG)-grafts have been synthesised, and their properties have been studied alongside those of the parent conjugated polymer (P3HT). Spectroelectrochemical and conductometric analyses revealed an early rise of the conductance of the polymers. Once spectral changes begin taking place, the conductance is stable, implying a loss of mobility of charge carriers, even though standard doping/dedoping patterns are observed. Prototype bulk heterojunction solar cells have been fabricated, based on P3HT/[6,6]-Phenyl-C61-butyric acid methyl ester (PCBM), as well as by substituting P3HT for each of the copolymers. The prototype solar cells achieved PCEs of up to 2.11%. This is one of the highest reported power conversion efficiency (PCE) for devices based on P3HT with low average molecular weight M_n = 12 kDa. Strong correlation between the structure of the copolymer and its photovoltaic performance was found. Elongation of PEG copolymer chain and the use of methyl group instead of terminal hydroxyl groups significantly improved photovoltaic performance. Full article

The fundamental understanding of the influence of molecular structure on the carrier transport properties in the field of organic thermoelectrics (OTEs) is a big challenge since the carrier transport behavior in conducting polymers reveals average properties contributed from all carrier transport channels, including those through intra-chain, inter-chain, inter-grain, and hopping between disordered localized sites. Here, combining molecular dynamics simulations and experiments, we investigated the carrier transport properties of doped highly oriented poly(3-hexylthiophene) (P3HT) films with different side-chain regioregularity. It is demonstrated that the substitution of side chains can not only take effect on the carrier transport edge, but also on the dimensionality of the transport paths and as a result, on the carrier mobility. Conductive atomic force microscopy (C-AFM) study as well as temperature-dependent measurements of the electrical conductivity clearly showed ordered local current paths in the regular side chain P3HT films, while random paths prevailed in the irregular sample. Regular side chain substitution can be activated more easily and favors one-dimensional transport along the backbone chain direction, while the irregular sample presents the three-dimensional electron hopping behavior. As a consequence, the regular side chain P3HT samples demonstrated high carrier mobility of 2.9 ± 0.3 cm²/V·s, which is more than one order of magnitude higher than that in irregular side chain P3HT films, resulting in a maximum thermoelectric (TE) power factor of 39.1 ± 2.5 μW/mK² at room temperature. These findings would formulate design rules for organic semiconductors based on these complex systems, and especially assist in the design of high performance OTE polymers. Full article