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Alkoxy side-chain tethered polyfluorene conjugated polyelectrolyte (CPE), poly[(9,9-bis((8-(3-methyl-1-imidazolium)octyl)-2,7-fluorene)-alt-(9,9-bis(2-(2-methoxyethoxy)ethyl)-fluorene)] dibromide (F8imFO4), is utilized to obtain CPE-hybridized ZnO nanoparticles (NPs) (CPE:ZnO hybrid NPs). The surface defects of ZnO NPs are passivated through coordination interactions with the oxygen atoms of alkoxy side-chains and the bromide anions of ionic pendent groups from F8imFO4 to the oxygen vacancies of ZnO NPs, and thereby the fluorescence quenching at the interface of yellow-emitting poly(p-phenylene vinylene)/CPE:ZnO hybrid NPs is significantly reduced at the CPE concentration of 4.5 wt%. Yellow-emitting polymer light-emitting diodes (PLEDs) with CPE(4.5 wt%):ZnO hybrid NPs as a cathode interfacial layer show the highest device efficiencies of 11.7 cd A−1 at 5.2 V and 8.6 lm W−1 at 3.8 V compared to the ZnO NP only (4.8 cd A−1 at 7 V and 2.2 lm W−1 at 6.6 V) or CPE only (7.3 cd A−1 at 5.2 V and 4.9 lm W−1 at 4.2 V) devices. The results suggest here that the CPE:ZnO hybrid NPs has a great potential to improve the device performance of organic electronics.

A molecular nano-floating gate (NFG) of pentacene-based transistor memory devices is developed using conjugated polymer nanoparticles (CPN) as the discrete trapping sites embedded in an insulating polymer, poly (methacrylic acid) (PMAA). The nanoparticles of polyfluorene (PF) and poly(fluorene-alt-benzo[2,1,3]thiadiazole (PFBT) with average diameters of around 50–70 nm are used as charge-trapping sites, while hydrophilic PMAA serves as a matrix and a tunneling layer. By inserting PF nanoparticles as the floating gate, the transistor memory device reveals a controllable threshold voltage shift, indicating effectively electron-trapping by the PF CPN. The electron-storage capability can be further improved using the PFBT-based NFG since their lower unoccupied molecular orbital level is beneficial for stabilization of the trapped charges, leading a large memory window (35 V), retention time longer than 104 s with a high ON/OFF ratio of >104. In addition, the memory device performance using conjugated polymer nanoparticle NFG is much higher than that of the corresponding polymer blend thin films of PF/polystyrene. It suggests that the discrete polymer nanoparticles can be effectively covered by the tunneling layer, PMAA, to achieve the superior memory characteristics.

In polyfluorenes it is generally accepted that (photo)degradation leads to fluorenone type defects that accept the excitation energy and emit green-to-yellow light with rather low efficiency. Although initial spectroscopic studies suggest the same to hold true for ladder-type poly(para-phenylene)s (LPPPs), kinetic studies of the degradation process are not compatible with the established mechanism. In general, the observed green emission can be caused by the introduction of carbonyl groups; however, only if associated with an additional disruption of the backbone rigidity and hence planarity of the entire π-system. This is clearly shown by comparison with synthesized model compounds, which are bearing the fluorenone motif yet possess very different optical properties as compared to the defects, which are actually formed. Degradation can be caused by solvent specific, yet substrate nonspecific aromatic formylation but mainly originates from reaction with in-situ generated singlet oxygen, both in solution as well as in thin films. Time-dependent photoluminescence measurements on thin films show that green emission is enhanced by energy transfer from intact molecules to defect centers.

Photovoltaics based on organic−inorganic perovskites offer new promise to address the contemporary energy and environmental issues. These solar cells have so far largely relied on small-molecule hole transport materials such as spiro-OMeTAD, which commonly suffer from high cost and low mobility. In principle, polyfluorene copolymers can be an ideal alternative to spiro-OMeTAD, given their low price, high hole mobility and good processability, but this potential has not been explored. Herein, polyfluorene derived polymers-TFB and PFB, which contain fluorine and arylamine groups, are demonstrated and can indeed rival or even outperform spiro-OMeTAD as efficient hole-conducting materials for perovskite solar cells. In particular, under the one-step perovskite deposition condition, TFB achieves a 10.92% power conversion efficiency that is considerably higher than that with spiro-OMeTAD (9.78%), while using the two-step perovskite deposition method, about 13% efficient solar cells with TFB (12.80%) and spiro-OMeTAD (13.58%) are delivered. Photo­luminescence reveals the efficient hole extraction and diffusion at the interface between CH3NH3PbI3 and the hole conducting polymer. Impedance spectroscopy uncovers the higher electrical conductivity and lower series resistance than spiro-OMeTAD, accounting for the significantly higher fill factor, photocurrent and open-circuit voltage of the TFB-derived cells than with spiro-MeOTAD.

Controlled Suzuki–Miyaura coupling polymerization of 7′-bromo-9′,9′-dioctyl-fluoren-2′-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane initiated by bromo(4-tert-butoxycarbonylamino-phenyl)(tri-tert-butylphosphine)palladium (1) or bromo(4-diethoxyphosphoryl-phenyl)(tri-tert-butylphosphine)palladium (2) yields functionalized polyfluorenes (Mn = 4 × 103 g mol−1, Mw/Mn < 1.2) with a single amine or phosphonic acid, respectively, end-group. High temperature synthesis of cadmium selenide quantum dots with these functionalized polyfluorenes as stabilizing ligands yields hybrid particles consisting of good quality (e.g. emission full width at half maximum of 30 nm; size distribution σ < 10%) inorganic nanocrystals with polyfluorene attached to the surface, as corroborated by transmission electron microscopy analysis and analytical ultracentrifugation. Sedimentation studies on particle dispersions show that a substantial portion (ca. half) of the phosphonic acid terminated polyfluorene ligands is bound to the inorganic nanocrystals, versus ca. 5% for the amino-functionalized polyfluorene ligands. Single particle micro-photoluminescence spectroscopy shows an efficient and complete energy transfer from the polyfluorene layer to the inorganic quantum dot.

The application of a time-resolved photoluminescence technique and fluorescence lifetime imaging microscopy for biosensing and bioimaging based on phosphorescent conjugated polyelectrolytes (PCPEs) containing Ir(III) complexes and polyfluorene units is reported. The specially designed PCPEs form 50 nm nanoparticles with blue fluorescence in aqueous solutions. Electrostatic interaction between the nanoparticles and heparin improves the energy transfer between the polyfluorene units to Ir(III) complex, which lights up the red signal for naked-eye sensing. Good selectivity has been demonstrated for heparin sensing in aqueous solution and serum with quantification ranges of 0–70 μM and 0–5 μM, respectively. The signal-to-noise ratio can be further improved through time-resolved emission spectra, especially when the detection is conducted in complicated environment, e.g., in the presence of fluorescent dyes. In addition to heparin sensing, the PCPEs have also been used for specific labeling of live KB cell membrane with high contrast using both confocal fluorescent cellular imaging and fluorescence lifetime imaging microscopies. This study provides a new perspective for designing promising CPEs for biosensing and bioimaging applications.

This work investigates the composition and morphology of films of poly(3-hexylthiophene) (P3HT), polyfluorene co-polymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl) (F8TBT) and blends thereof that are used in efficient all-polymer solar cells. Ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS) studies on thin polymer and blend films on ZnO substrates reveal the existence of a 1–2 nm thick P3HT layer at the top surface of the blend films. XPS depth profiling studies reveal a density wave (λ ≈ 70 nm) originating from the air interface. As no preferential accumulation is observed at the bottom interface with ZnO, the composition at this interface is consistent with the original composition of the blend solution prior to spin-coating. The morphology of this buried interface was studied by means of atomic force microscopy (AFM) and revealed that upon annealing the average domain size increases slightly (from 27 nm to 40 nm). It is observed that the photovoltaic performance of such inverted hybrid device improves upon annealing, however we believe this to mostly be a result of increased crystallinity in the P3HT domains leading to improved charge transport in the device, rather than changes in the blend phase separation.

The charge transport and recombination in white-emitting polymer light- emitting diodes (PLEDs) are studied. The PLED investigated has a single emissive layer consisting of a copolymer in which a green and red dye are incorporated in a blue backbone. From single-carrier devices the effect of the green- and red-emitting dyes on the hole and electron transport is determined. The red dye acts as a deep electron trap thereby strongly reducing the electron transport. By incorporating trap-assisted recombination for the red emission and bimolecular Langevin recombination for the blue emission, the current and light output of the white PLED can be consistently described. The color shift of single-layer white-emitting PLEDs can be explained by the different voltage dependencies of trap-assisted and bimolecular recombination. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of on-chain ketone defects on the charge transport of the polyfluorene derivative poly(9,9-dioctylfluorene) (PFO) is investigated. Using MoO3 as ohmic hole contact, the hole transport in a pristine PFO diode is observed to be limited by space-charge, whereas fluorenone contaminated PFO (PFO-F) is shown to be trap limited by the occurrence of an exponential trap distribution with a trap depth of 0.18 eV. The electron transport in PFO is also observed to be trap limited, but in order to describe the electron transport of PFO-F, an additional trap level with a depth of 0.46 eV must be introduced. The obtained energy levels of the fluorenone trapping sites are in close agreement with cyclic voltammetry (CV) measurements reported in literature. As a result, the fluorenone defects are shown to simultaneously act as hole- and electron trap. Moreover, through ideality factor measurements, the green emission associated with these defects is observed to originate from trap-assisted recombination. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A study of an efficient blue light-emitting diode based on a fluorescent aryl polyfluorene (aryl-F8) homopolymer in an inverted device architecture is presented, with ZnO and MoO3 as electron- and hole-injecting electrodes, respectively. Charge-carrier balance and color purity in these structures are achieved by incorporating poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)-diphenylamine (TFB) into aryl-F8. TFB is known to be a hole-transporting material but it is found to act as a hole trap on mixing with aryl-F8. Luminance efficiency of ≈6 cd A−1 and external quantum efficiency (EQE) of 3.1% are obtained by adding a small amount (0.5% by weight) of TFB into aryl-F8. Study of charge injection and transport in the single-carrier devices shows that the addition of a small fraction of hole traps is necessary for charge-carrier balance. Optical studies using UV–vis and fluorescence spectroscopic measurements, photoluminescence quantum yield, and fluorescence decay time measurements indicate that TFB does not affect the optical properties of the aryl-F8, which is the emitting material in these devices. Luminance efficiency of up to ≈11 cd A−1 and EQE values of 5.7% are achieved in these structures with the aid of improved out-coupling using index-matched hemispheres.

A series of water-soluble polyfluorene derivatives containing diketopyrrolopyrrole derivative units are synthesized and characterized. These copolymers, poly[9,9'-bis(6”-N,N,N-trimethyl ammonium) hexylfluorene-co-alt-2,5-bis (6”-N,N,N-trimethylammonium)hexylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] (PFDPN), demonstrate intramolecular energy transfer from the fluorene units to the diketopyrrolopyrrole derivative units, and show red-shifted emissions in aqueous solution. The PFDPN polymers can combine with Cy5-labeled ssDNA by electrostatic interactions and efficiently amplify the fluorescence signal of red Cy5 dye through fluorescence resonance energy transfer. Moreover, based on DNA replacement method, this amplification system can be used to monitor the template-independent DNA elongation process catalyzed by terminal deoxynucleotidyl transferase.

The metastable β-phase morphology, inherent to most polyfluorene homo-polymers, is of interest due to its superior optical and electrical characteristics compared to its amorphous analogue. Here, a polyfluorene with vinyl-ether-functionalized aliphatic side-chains that allow crosslinking is reported. It is demonstrated that the previously induced conformational morphology is preserved in the resulting polyfluorene network, which enables subsequent wet thin-film processing. Electron-beam lithography provides a means for sub-(optical)-wavelength patterning of the crosslinkable polyfluorene films. As a specific demonstration, optically-pumped distributed-feedback (DFB) lasers made from surface-relief gratings in amorphous and β-phase polyfluorene are presented. By backfilling gratings of one morphology by the other, devices are demonstrated that exhibit lasing at two wavelengths with a threshold (

The charge transport in blue light-emitting polyspirobifluorene is investigated by both steady-state current-voltage measurements and transient electroluminescence. Both measurement techniques yield consistent results and show that the hole transport is space-charge limited. The electron current is found to be governed by a high intrinsic mobility in combination with electron traps. Numerical simulations on light-emitting diodes reveal a shift in the recombination zone from the cathode to the anode with increasing bias. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We utilize transient techniques to directly compare the operation of polymer/fullerene, polymer/nanocrystal, and polymer/polymer bulk heterojunction solar cells. For all devices, poly(3-hexylthiophene) (P3HT) is used as the electron donating polymer, in combination with either the fullerene derivative phenyl-C(61)-butyric acid methyl ester (PCBM) in polymer/fullerene cells, CdSe nanoparticles in polymer/nanocrystal cells, or the polyfluorene copolymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3- benzothiadiazole]-2,2-diyl) (F8TBT) in polymer/polymer cells. Transient photocurrent and photovoltage measurements are used to probe the dynamics of charge-separated carriers, with vastly different dynamic behavior observed for polymer/fullerene, polymer/polymer, and polymer/nanocrystal devices on the microsecond to millisecond timescale. Furthermore, by employing transient photocurrent analysis with different applied voltages we are also able to probe the dynamics behavior of these cells from short circuit to open circuit. P3HT/F8TBT and P3HT/CdSe devices are characterized by poor charge extraction of the long-lived carriers attributed to charge trapping. P3HT/PCBM devices, in contrast, show relatively trap-free operation with the variation in the photocurrent decay kinetics with applied bias at low intensity, consistent with the drift of free charges under a uniform electric field. Under solar conditions at the maximum power point, we see direct evidence of bimolecular recombination in the P3HT/PCBM device competing with charge extraction. Transient photovoltage measurements reveal that, at open circuit, photogenerated charges have similar lifetimes in all device types, and hence, the extraction of these long-lived charges is a limiting process in polymer/nanocrystal and polymer/polymer devices.

Here, we report on the dual functionality of tungsten oxide for application as an efficient electron and hole injection/transport layer in organic light-emitting diodes (OLEDs). We demonstrate hybrid polymer light-emitting diodes (Hy-PLEDs), based on a polyfluorene copolymer, by inserting a very thin layer of a partially reduced tungsten oxide, WO2.5, at the polymer/Al cathode interface to serve as an electron injection and transport layer. Significantly improved current densities, luminances, and luminous efficiencies were achieved, primarily as a result of improved electron injection at the interface with Al and transport to the lowest unoccupied molecular orbital (LUMO) of the polymer, with a corresponding lowering of the device driving voltage. Using a combination of optical absorption, ultraviolet spectoscopy, X-ray photoelectron spectroscopy, and photovoltaic open circuit voltage measurements, we demonstrate that partial reduction of the WO3 to WO2.5 results in the appearance of new gap states just below the conduction band edge in the previously forbidden gap. The new gap states are proposed to act as a reservoir of donor electrons for enhanced injection and transport to the polymer LUMO and decrease the effective cathode workfunction. Moreover, when a thin tungsten oxide film in its fully oxidized state (WO3) is inserted at the ITO anode/polymer interface, further improvement in device characteristics was achieved. Since both fully oxidized and partially reduced tungsten oxide layers can be deposited in the same chamber with well controlled morphology, this work paves the way for the facile fabrication of efficient and stable Hy-OLEDs with excellent reproducibility.

A fluorescent film sensor was prepared by chemical modification of a polyfluorene derivative on a glass-plate surface. X-ray photoelectron spectroscopy and ellipsometry measurements demonstrate the covalent attachment of the polyfluorene derivative to the glass-plate surface. The sensor was used to detect Cu2+ ions in aqueous solution by a mechanism exploiting fluorescence quenching of conjugated polymers. Among the tested metal ions, the film sensor presents good selectivity towards Cu2+ ions. Further experiments show that the sensing process is reversible. Moreover, sensory microarrays based on conjugated polymers targeting Cu2+ ions are constructed, which display similar sensing performance to that of the film sensor. The structural motif in which conjugated polymers are covalently confined to a solid substrate surface offers several attractive advantages for sensing applications. First, in comparison with film sensors in which small fluorescent molecules are employed as sensing elements, the sensitivity of our new film sensor is enhanced due to the signal-amplifying effect of the conjugated polymers. Second, the film sensors or microarrays can be used in aqueous environments, which is crucial for their potential use in a wide range of real-world systems. Since the sensing process is reversible, the sensing materials can be reused. Third, unlike physically coated polymer chains, the covalent attachment of the grafted chains onto a material surface precludes desorption and imparts long-term stability of the polymer chains.

Through controlled annealing of planar heterojunction (bilayer) devices based on the polyfluorene copolymers poly(9,9-dioctylfluorene-co-bis(N,N′-(4,butylphenyl))bis(N,N′-phenyl-1,4-phenylene)diamine) (PFB) and poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) we study the influence of interface roughness on the generation and separation of electron–hole pairs at the donor/acceptor interface. Interface structure is independently characterized by resonant soft X-ray reflectivity with the interfacial width of the PFB/F8BT heterojunction observed to systematically increase with annealing temperature from 1.6 nm for unannealed films to 16 nm with annealing at 200 °C for ten minutes. Photoluminescence quenching measurements confirm the increase in interface area by the three-fold increase in the number of excitons dissociated. Under short-circuit conditions, however, unannealed devices with the sharpest interface are found to give the best device performance, despite the increase in interfacial area (and hence the number of excitons dissociated) in annealed devices. The decrease in device efficiency with annealing is attributed to decreased interfacial charge separation efficiency, partly due to a decrease in the bulk mobility of the constituent materials upon annealing but also (and significantly) due to the increased interface roughness. We present results of Monte Carlo simulations that demonstrate that increased interface roughness leads to lower charge separation efficiency, and are able to reproduce the experimental current-voltage curves taking both increased interfacial roughness and decreased carrier mobility into account. Our results show that organic photovoltaic performance can be sensitive to interfacial order, and heterojunction sharpness should be considered a requirement for high performance devices.

Three kinds of red electroluminescent (EL) polymers based on polyfluorene as blue host and 2,1,3-benzothiadiazole derivatives with different emission wavelengths as red dopant units on the side chain are designed and synthesized. The influence of the photoluminescence (PL) efficiencies and emission wavelengths of red dopants on the EL efficiencies and color purities of the resulting polyfluorene copolymers of dopant/host system is investigated by adjusting the electron donating ability of the donor units in D-pi-A-D typed 2,1,3-benzothiadiazole derivatives. The devices of these red-emitting polymers realize remarkable EL efficiency/color purity trade-offs. The single-layer devices with the configuration of ITO/PEDOT:PSS/Polymer/Ca/Al show pure red emission at 624 nm with a luminous efficiency of 3.83 cd A(-1) and CIE of (0.63, 0.35) for PFR1, saturated red emission at 636 nm with a luminous efficiency of 2.29 cd A(-1) and CIE of (0.64, 0.33) for PFR2, respectively. By introduction of an additional electron injection layer PF-EP(Ethanol soluble phosphonate-functionalized polyfluorene), high performance pure and saturated red emission two-layer devices (ITO/PEDOT:PSS/Polymer/PF-EP/LiF/Al) were achieved with maximum luminous efficiencies of 5.50 cd A(-1) and CIE of (0.62, 0.35) for PFR1, 3.10 cd A(-1) and CIE of (0.63, 0.33) for PFR2, respectively, which are the best results for pure and saturated fluorescent red EL polymers reported so far.

We report an efficient non-doped all-polymer polymer white-light-emitting diode (PWLED) with a fluorescent three-color, white single polymer as an emissive layer, an ethanol-soluble phosphonate-functionalized polyfluorene (PF-EP) as an electron-injection/electron-transport layer, and LiF/Al as a cathode, respectively. The all-polymer PWLED achieves a peak external quantum efficiency of 6.7%, a forward viewing luminous efficiency of 15.4 cd A(-1) and a power efficiency of 11.4 lm W-1, respectively, at a brightness of 347 cd m(-2) with Commission Internationale d'Eclairage coordinates of (0.37, 0.42) and color rendering index of 85, which is the best results among the non-doped PWLEDs. Moreover, this kind of PWLED not only shows excellent color stability, but also achieves high brightness at low voltages. The brightness reaches 1000, 10000, and 46830 cd m(-2) at voltages of 4.5, 5.4, and 7.5 V, respectively. The significant enhancement of white-single-polymer-based PWLEDs with PF-EP/LiF/Al to replace for the commonly used Ca/Al cathode is attributed to the more efficient electron injection at PF-EP/LiF/Al interfaces, and the coordinated protecting effect of PF-EP from diffusion of Al atoms into the emissive layer and exciton-quenching near cathode interfaces. The developed highly efficient non-doped all-polymer PWLEDs are well suitable for solution-processing technology and provide a huge potential of low-cost large-area manufacturing for PWLEDs.

The fabrication of high-resolution nanostructures in both poly(p-phenylene vinylene), PPV, and a crosslinkable derivative of poly(9,9'-dioctylfluorene), F8, using scanning near-field optical lithography, is reported. The ability to draw complex, reproducible structures with 65000 pixels and lateral resolution below 60 nm (< lambda/5) is demonstrated over areas up to 20 mu m x 20 mu m. Patterning on length-scales of this order is desirable for realizing applications both in organic nanoelectronics and nanophotonics. The technique is based on the site-selective insolubilization of a precursor polymer under exposure to the confined optical field present at the tip of an apertured near-field optical fiber probe. In the case of PPV, a leaving-group reaction is utilized to achieve insolubilization, whereas the polyfluorene is insolubilized using a photoacid initiator to create a crosslinked network in situ. For PPV, resolubilization of the features is observed at high exposure energies. This is not seen for the crosslinked F8 derivative, r-F8Ox, allowing us to pattern structures up to 200 nm in height.

Distributed feedback organic semiconductor lasers based on polyfluorene are shown to be suitable for use as chemical sensors for the detection of nitroaromatic-based explosive vapors. The laser threshold is increased by a factor of 1.8 and the slope efficiency is reduced by a factor of 3 after exposure to the vapor. The sensing efficiency depends strongly on the excitation energy with a maximum efficiency of 85%. The temporal dynamics of the laser response to the analyte have been investigated. The laser emission falls to 60% of its initial value in 46 s. A model is developed to offer some insight into the diffusion of the vapor molecules inside the polymer layer.

Semiconducting single-walled carbon nanotubes (sc-SWCNTs) enriched by a conjugated polymer extraction process have been actively studied for various applications in both electronics and optoelectronics. Although the resulting tube samples usually have high sc-purity and concentration, SWCNT networks from such dispersions typically contain residual conjugated polymer that may degrade device performance and its removal remains a challenge while maintaining uniform, dense SWCNT thin film networks. In this study, a novel polymer–SWCNT combination based on an alternating bisfuran-s-tetrazine and benzo[1,2-b:4,5-b′]dithiophene copolymer abbreviated as PBDTFTz is proposed. This polymer decomposes at >250 °C or under UV irradiation. In situ transistor characterization under laser irradiation confirms the polymer decomposition. The study of the tube network in the transistor channel at various channel lengths reveals significantly reduced contact resistance attributed to removal of the wrapping PBDTFTz polymer. In ammonia sensing experiments, sc-SWCNT networks demonstrate rapid and reversible responses, while the unwrapped nanotube networks prove superior in terms of signal to noise ratio and a detection limit of 2.5 ppb is calculated, almost four times better than polymer wrapped nanotubes.

Here, the optical properties of a series of structurally well-defined model compounds for oxidatively degraded poly(dialkylfluorenes) (PFs) are reported. Specifically, linear compounds comprising one, two, or four dihexylfluorene (F) moieties together with one fluorenone (O) moiety placed either at the end or in the center of each chain (i.e., FO, FFO, FOF, FFOFF) are studied. The results support the recent observation that the photophysics of the fluorenone-centered "pentamer" (FFOFF) is most similar to that of oxidized PFs. They further demonstrate that molecule―molecule interaction is essential to activate the green emission band. Investigations by X-ray diffraction (XRD) identify the solid-state structure of a representative member of this class of compounds and reveal inter-molecular interaction through dipole―dipole coupling between neighboring fluorenone moieties.

The charge transport and photogeneration in solar cells based on the low bandgap-conjugated polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H- cyclopenta[2,1-b; 3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and fullerenes is studied. The efficiency of the solar cells is limited by a relatively low fill factor, which contradicts the observed good and balanced charge transport in these blends. Intensity dependent measurements display a recombination limited photocurrent, characterized by a square root dependence on effective applied voltage, a linear dependence on light intensity and a constant saturation voltage. Numerical simulations show that the origin of the recombination limited photocurrent stems from the short lifetime of the bound electron-hole pairs at the donon/acceptor interface.

A description of the synthesis of random (9,9-dioctylfluorene-2,7-diyl)–(dibenzothiophene-S,S-dioxide-3,7-diyl) co-polymers (p(F-S)x) by palladium-catalyzed Suzuki cross-coupling polymerization where the feed ratio of the latter is varied from 2 to 30 mol % (i.e., x = 2–30) is given. Polymer light emitting devices are fabricated with the configuration indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid)/p(F–S)x/Ba/Al. The device external quantum efficiency increased as the ratio of the S co-monomer was increased, up to a maximum of 1.3% at 100 mA cm−2 for p(F-S)30 and a brightness of 3 770 cd m−2 (at 10 V). The S units impart improved electron injection, more balanced mobilities, and markedly improved device performance compared to poly(9,9-dioctylfluorene) under similar conditions. These co-polymers display broad emission, observed as greenish-white light, which arises from dual fluorescence, viz. both local excited states and charge transfer states. Utilizing dual emission can reduce problems associated with Forster energy transfer from high-energy to-low energy excited states.

Neutron reflectivity and photoluminescence measurements are reported on bilayers of polyfluorene-based conjugated polymers. By using a novel thermal processing procedure it is possible to control the width of the interface between poly(9,9-dioctylfluorene) (F8) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT), and measure the impact of interfacial roughness on the resonant energy transfer of excitons at the interface (Forster transfer). It is found that increasing the root mean square (rms) roughness of the F8/F8BT interface over the range of ∼1 nm to ∼5 nm leads to a greatly enhanced Forster transfer from F8 to F8BT molecules. By comparing photoluminescence measurements with simple calculations it is concluded that the level of enhancement of the F8BT peak at rough interfaces can only be adequately explained if mixing of F8 and F8BT at a molecular level dominates over the interfacial roughness due to thermally excited capillary waves.

Di-n-alkyl substituted polyfluorenes with alkyl chain lengths of 6, 7, 8, 9, and 10 carbon atoms (PF6, PF7, PF8, PF9, and PF10) are studied in dilute solution in MCH using optical spectroscopy. Beta-phase is formed upon cooling in solutions (∼ 7 µg mL−1) of PF7, PF8, and PF9 only, which is observed as an equilibrium absorption peak at ∼ 437 nm and strong changes in the emission spectra. Beta-phase is formed upon thermal cycling to low temperature in solutions (∼7 µg mL−1) of PF7, PF8, and PF9, which is observed as an equilibrium absorption peak at ∼ 437 nm and strong changes in the emission spectra. Beta phase is found to occur more favorably in PF8 than in PF7 or PF9, which is attributed to a balance between two factors. The first is the dimer/aggregate formation efficiency, which is poorer for longer (more disordered) alkyl chain lengths, and the second is the Van der Waals bond energy available to overcome the steric repulsion and planarize the conjugated backbone, which is insufficient in the PF6 with a shorter alkyl chain. Beta phase formation is shown to be a result of aggregation, not a precursor to it. A tentative value of the energy required to planarize the fluorene backbone of (15.6 ± 2.5) kJ mol−1 monomer is suggested. Excitation spectra of PF6, PF7, PF8, and PF9 in extremely dilute (∼ 10 ng mL−1) solution show that beta phase can form reversibly in dilute solutions of PF7, PF8 and PF9, which is believed to be a result of chain collapse or well dispersed aggregates being present in solution from dilution of more concentrated solutions. PF7, PF8, and PF9 also form beta phase in thermally cycled solid films spin-cast from MCH. However, in the films the PF7 formed a larger fraction of beta phase than the PF9, in contrast to the case in solutions, because it is less likely that the close-packed chains in the solid state will allow the formation of planarized chains with the longer PF9 side chains.

Strong intermolecular interactions usually result in decreases in solubility and fluorescence efficiency of organic molecules. Therefore, amorphous materials are highly pursued when designing solution-processable, electroluminescent organic molecules. In this paper, a non-planar binaphthyl moiety is presented as a way of reducing intermolecular interactions and four binaphthyl-containing molecules (BNCMs): green-emitting BBB and TBT as well as red-emitting BTBTB and TBBBT, are designed and synthesized. The photophysical and electrochemical properties of the molecules are systematically investigated and it is found that TBT, TBBBT, and BTBTB solutions show high photoluminescence (PL) quantum efficiencies of 0.41, 0.54, and 0.48, respectively. Based on the good solubility and amorphous film-forming ability of the synthesized BNCMs, double-layer structured organic light-emitting diodes (OLEDs) with BNCMs as emitting layer and poly(N-vinylcarbazole) (PVK) or a blend of poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] and PVK as hole-transporting layer are fabricated by a simple solution spin-coating procedure. Amongst those, the BTBTB based OLED, for example, reaches a high maximum luminance of 8315 cd · m−2 and a maximum luminous efficiency of 1.95 cd · A−1 at a low turn-on voltage of 2.2 V. This is one of the best performances of a spin-coated OLED reported so far. In addition, by doping the green and red BNCMs into a blue-emitting host material poly(9,9-dioctylfluorene-2,7-diyl) high performance white light-emitting diodes with pure white light emission and a maximum luminance of 4000 cd · m−2 are realized.

Amplified spontaneous emission (ASE) of a series of blue-emitting poly(ladder-type phenylene)s (LPPP)s has been studied in thin film polymer waveguide structures. The chemically well-defined step-ladder polymers consist of an increasing number of bridged phenylene rings per monomer unit starting from fully arylated poly(ladder-type indenofluorene) up to poly(ladder-type pentaphenylene). The ASE characteristics of the polymers including the onset threshold values for ASE, the gain and loss coefficients as well as the photoluminescence (PL) properties, i.e., the solid state fluorescence lifetimes, decay kinetics and solid state quantum efficiencies have been studied by time-resolved PL spectroscopy. A fully arylated polyfluorene has been synthesized and its photophysical properties were compared to the step-ladder polymers. Steady-state photoinduced absorption and ultrafast transient absorption spectroscopy have been used to study excited state absorption of singlet and triplet states and polarons present in the solid state. The results demonstrate a minimum regarding the onset threshold value of ASE for a fully arylated poly(ladder-type indenofluorene) and a successive increase of the ASE threshold for the step-ladder polymers with more bridged phenylene rings. In particular, carbazole-containing step-ladder LPPPs exhibit significantly increased ASE threshold values as compared to their carbazole-free analogues due to a pronounced overlap of stimulated emission (SE) and photoinduced absorption (PA).

Here the influence of annealing on the operational efficiency of all-polymer solar cells based on blends of the polymers poly(3-hexylthiophene) (P3HT) and poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthiophen-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl) (F8TBT) is investigated. Annealing of completed devices is found to result in an increase in power conversion efficiency from 0.14 to 1.20%, while annealing of films prior to top electrode deposition increases device efficiency to only 0.19% due to a lowering of the open-circuit voltage and short-circuit current. By studying the dependence of photocurrent on intensity and effective applied bias, annealing is found to increase charge generation efficiency through an increase in the efficiency of the separation of bound electron-hole pairs following charge transfer. However, unlike many other all-polymer blends, this increase in charge separation efficiency is not only due to an increase in the degree of phase separation that assists in the spatial separation of electron-hole pairs, but also due to an order of magnitude increase in the hole mobility of the P3HT phase. The increase in hole mobility with annealing is attributed to the ordering of P3HT chains evidenced by the red-shifting of P3HT optical absorption in the blend. We also use X-ray photoelectron spectroscopy (XPS) to study the influence of annealing protocol on film interface composition. Surprisingly both top and bottom electrode/blend interfaces are enriched with P3HT, with the blend/top electrode interface consisting of more than 95% P3HT for as-spun films and films annealed without a top electrode. Films annealed following top electrode deposition, however, show an increase in F8TBT composition to ∼15%. The implications of interfacial composition and the origin of open-circuit voltage in these devices are also discussed.

Electrophosphorescent copolymers have been synthesized by covalent bonding of a red-emitting osmium complex Os(bpftz), which contains two 3-trifluoromethyl-5-(4-tert-butyl-2-pyridyl)triazolate (bpftz) cyclometalated ligands, into the backbone of a bipolar polyfluorene (PF) copolymer. Employing these copolymers, a highly efficient red polymer light-emitting diode has been realised that has an external quantum efficiency of 18.0%, a maximum brightness of 38000cdm � 2 , and an emission centered at 618nm. In addition, after incorporating appropriate amounts of green-emitting benzothiadiazole (BT) and the aforementioned Os(bpftz) into the bipolar PF, an efficient white-light electroluminescent polymer is obtained that displays simultaneous blue, green, and red emissions.

The preparation and properties of an electrochemically crosslinked Au nanoparticle/polyvinylcarbazole (PVK)/polyfluorene (PFC) nanocomposite film is described. Blends of the blue-light emitting PFC, PVK, and the 11-(9H-carbazol-9-yl)-undecane-1-thiol-capped Au nanoparticles (CBZ-S-Au) were prepared as thin films by spin-coating and subsequent crosslinking by cyclic voltammetry (CV). The electrochemical properties are then evaluated on the basis of the redox behavior (reversibility) and electron-transport properties of the films. They are further characterized by UV-vis spectroscopy, photoluminescence spectroscopy, and atomic force microscopy (AFM). The large differences in photoluminescence properties of the CBZ-S-Au/PFCVK crosslinked copolymer composite film compared to the PFCVK polymer alone result in an efficient energy-transfer system, in which the excimer peak is almost totally quenched. This indicates a compatible match between the absorbance of the Au plasmons and the emission of the excimer energy trap from PF polymers. Furthermore, electrochemical crosslinking enhances this match both by shifting the absorbance to greater overlap and decreasing the Forster distance between the Au nanoparticle and the PFCVK polymer chains.

A novel series of kinked star-shaped oligofluorene/triazatruxene hybrids are conveniently prepared via a powerful microwave-enhanced multiple coupling methodology. Constructing kinked star-shaped architectures can effectively suppress crystallization and aggregation. The resulting materials are highly amorphous, showing stable amorphous morphology against crystallization. A triazatruxene core endows the materials with elevated highest occupied molecular orbital (HOMO) levels that are well matched to the anode work function, leading to a significantly improved hole-injection property. They hybrids are highly luminescent in both solution (quantum yield is 0.52-0.80) and the solid-state (quantum yield is 0.45-0.76) with bright blue emission. Remarkably, solution-processed devices displaying single-layer electroluminescence (EL) based on these oligomers exhibit efficient blue EL and demonstrate striking color stability, almost unchanged with increasing driving voltage. The best device performance has a rather low turn-on voltage (3.3 V) and a high device efficiency (2.16 % @ 2382 cd m -2 ) as well as a high brightness (7714 cd m -2 @ 10 V) with CIE coordinates of (0.16, 0.15); it shows remarkably better EL performance than devices based on linear oligofluorene or polyfluorene counterparts. The results prove that an oligomer with kinked star-shaped architecture is extremely promising for efficient and stable blue EL. The reasons for the enhanced functional properties and the improved color stability are discussed in relation to the chemical structures and components.

A New Donor-Acceptor-Donor Polyfluorence Copolymer with Balanced Electron and Hole Mobility

Two fluorescent molecules with an alkynylanthracene core and pyrene end-cappers have been synthesized and fully characterized. Carbazole moieties are introduced into one molecule at the C9 position of the fluorene linkages to enhance the hole-transport ability of the molecule and to reduce intermolecular interactions. Both compounds exhibit high thermal stabilities and narrow energy bandgaps. Single-layer polymer light-emitting diodes (PLEDs) based on poly(9,9-dioctylfluorene) (PFO) doped with the synthesized compounds exhibit excellent performance. A PLED with 0.2 % of dopant 7 had a high luminance efficiency of 10.7 ± 0.3 cd A–1 as well as a brightness of 1400 cd m–2 at a current density of 13 mA cm–2, and a low turn on voltage (3.1 V) at a brightness of 10 cd m–2. A maximum brightness of 20 500 ± 1400 cd m–2 at 7 V was also measured. The high efficiency of the device's performance is attributed to the good electron and hole trapping ability of the dopants, which possess suitable energy levels as compared to those of PFO.

The photophysical properties of blends of fluorene copolymer and the fullerene derivative PCBM are analyzed with a particular attention to photovoltaic applications. The properties of the blends are determined by the relative alignment of the HOMO energy levels. In the blend where the HOMO levels of the copolymer and the fullerene are aligned there is not signature of charge stabilization and photovoltaic effect. While in the blend where there is an offset between the HOMO levels the charge stabilization is accompanied by good photovoltaic performances. The photoluminescence spectrum of the latter blend is characterized by the appearance of a new peak at low energy with a lifetime of a few ns that red-shifts with the increase of the PCBM percentage. The feature is attributed to the emission from a charge-transfer exciton that is red-shifted by the change of dielectric constant of the medium.

An efficient white-light-emitting polymer (W3) is realized by covalently attaching a green fluorophore and a red phosphor into the backbone and the side chains, respectively, of polyfluorene at a concentration of 0.04 mol %. In addition, charge-transport-ing pendant units are included to improve carrier injection and transport. White-electrophosphorescent devices with the structure ITO/PEDOT:PSS/W3/CsF/Al (ITO: indium tin oxide; PEDOT:PSS: poly(styrenesulfonate)-doped poly(3,4-ethylene-dioxythiophene)) exhibit a low turn-on voltage of 2.8 V and a luminance of ca. 10 3 cd m -2 at below 6 V. The peak luminance and power-conversion efficiencies are 8.2 cd A -1 and 7.2 1m W 4 -1 respectively. Furthermore, the device shows relatively stable white emission: the Commission Internationale d'Eclairage (CIE) chromaticity coordinates of the devices change only slightly from (0.35,0.38) at 10 mA cm -2 to (0.33,0.36) at 100 mA cm -2 , with an almost constant color render index (CRI) value of 82 at all measured current densities.

Evidence is presented for the formation of a weak ground-state charge-transfer complex in the blend films of poly[9,9-dioctylfluorene-co-N-(4-methoxyphenyl)diphenylamine] polymer (TFMO) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM), using photothermal deflection spectroscopy (PDS) and photoluminescence (PL) spectroscopy. Comparison of this polymer blend with other polyfluorene polymer/PCBM blends shows that the appearance of this ground-state charge-transfer complex is correlated to the ionization potential of the polymer, but not to the optical gap of the polymer or the surface morphology of the blend film. Moreover, the polymer/PCBM blend films in which this charge-transfer complex is observed also exhibit efficient photocurrent generation in photovoltaic devices, suggesting that the charge-transfer complex may be involved in charge separation. Possible mechanisms for this charge-transfer state formation are discussed as well as the significance of this finding to the understanding and optimization of polymer blend solar cells.

The problem of phosphorescence quenching by the host polymer of a dopant in a polyfluorene-based electrophosphorescent device has been extensively studied. This paper concentrates on reduction of the rate of triplet-energy transfer from the dopant to the host by making inert (-butyl substitutions to the ligands of the well-understood fac-trisphenylpyridine iridium phosphorescent dopant. These substitutions introduce steric bulk to the dopant that approximately halves the rate of energy transfer compared to the unsubstituted dopant, and a concomitant increase in device performance is observed. This is attributed to the strong distance dependence of the Dexter-type energy transfer involved, the steric bulk of the t-butyl groups effectively preventing the energy transfer from emissive dopant to the host. In addition, through the use of specific substitutions on either the pyridyl or phenyl ring, the pathway of the energy transfer has been identified as being through the pyridyl ring of the ligand. Employing this technique of steric prevention of the triplet-energy transfer to the host reduces the need for development of hosts with a high triplet level for electrophosphorescent devices.

We have prepared highly luminescent dendron-substituted copolyfluorenes that incorporate surface-modified cadmium sulfide nanoparticles. Both the photoluminescence and electroluminescence efficiencies of the polymer nanocomposites are dramatically enhanced relative to the values of the pure polymer.

In this study a blue-light-emitting conjugated polymer, poly(9,9-dioctylfluorene), is confined to the interlayer space of inorganic, layered metal dichalcogenide materials, metallic MoS2, and semiconducting SnS2. The nanocomposites are prepared through Li intercalation into the inorganic compound, exfoliation, and restacking in the presence of the polymer. X-ray diffraction and optical absorption measurements indicate that a single conjugated polymer monolayer, with an overall extended planar morphology conformation, is isolated between the inorganic sheets, so that polymer aggregation or p–p interchain interactions are significantly reduced. Photoluminescence (PL) measurements show that the appearance of the undesirable green emission observed in pristine polymer films is suppressed by incorporating the polymer into the inorganic matrix. The blue emission of the intercalated polymer is stable for extended periods of time, over two years, under ambient conditions. Furthermore, the green emission is absent in the PL spectra of nanocomposite films heated at 100°C for 7 h in air with direct excitation of the keto defect. Finally, no green emission was observed in the electroluminescence spectrum of light-emitting devices fabricated with a polymer-intercalated SnS2 nanocomposite film. These results support the proposed hypothesis that fluorenone defects alone are insufficient to generate the green emission and that interchain interactions are also required.

New single-polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λmax = 421 nm/445 nm) and orange emission (λmax = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m–2, luminance efficiency of 7.30 cd A–1, and power efficiency of 3.34 lm W–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8-naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single-layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn-on voltage of 3.5 V, luminance efficiency of 8.99 cd A–1, power efficiency of 5.75 lm W–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m–2. This performance is roughly comparable to that of white organic light-emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.

The influence of the solvent on the morphol. and performance of polymer solar cells was studied in devices based on blends of the polyfluorene copolymer, poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2', 1',3'-benzothiadiazole)), and [6,6]-phenyl-C61-butyric acid Me ester. The blends are spin-coated from CHCl3 or from CHCl3 mixed with small amts. of xylene, toluene, or chlorobenzene. The devices are characterized under monochromatic light and AM1.5 solar illumination. An enhancement of the photocurrent d. was obsd. in diodes made from CHCl3 mixed with chlorobenzene, and a decreased photocurrent d. is obsd. in diodes made from CHCl3 mixed with xylene or toluene, compared to diodes made from neat CHCl3. The open-circuit voltages are almost the same for all diodes. The surfaces of the active layers were imaged with AFM. Height images indicate that a finer and more uniform distribution of domains corresponds to the diodes with enhanced photocurrent that are made from CHCl3 mixed with chlorobenzene, while a structure with larger domains is assocd. with the lower photocurrents in the diodes made from CHCl3 mixed with xylene or toluene. The influence of the morphol. on the excited-state dynamics and charge generation was studied using time-resolved spectroscopy. Fast formation of bound charge pairs followed by their conversion into free charge carriers was resolved, and excitation-intensity-dependent non-geminate recombination of free charges was obsd. A significant enhancement in free-charge-carrier generation was obsd. on introducing chlorobenzene into CHCl3. Imaging photocurrent generation from the solar cells with a light-pulse technique shows an inhomogeneous photocurrent distribution, which is related to the undulations in the thickness of the active layer. Thicker parts of the diodes yield higher photocurrent values. [on SciFinder (R)]

The emission of semiconducting polyfluorenes is often accompanied by an undesired feature in the green spectral region. Whereas a number of previous investigations have argued in favor of a monomolecular origin of the emission species based on ketonic defects, recent experimental results suggested the necessity of excimer formation between individual fluorenone units. We provide a range of new evidence supporting the monomolecular origin of green band emission in polyfluorenes. Most importantly, we succeed in performing single-molecule spectroscopy on fluorenone-containing polyfluorene model compounds. Whereas most fluorenone-containing molecules exhibit both blue backbone and green fluorenone emission independent of fluorenone concentration, it is the relative intensities of the two species which correlate strongly with the fluorenone concentration on the single-molecule level. Furthermore, we consider a novel model compound with a bifacial arrangement of two fluorenone units. This compound does not provide any signatures of enhanced intramolecular excimer formation but does strongly indicate that concentration quenching effects occur once fluorenone units can interact electronically. The ability to detect on-chain defect emission in a single polymer molecule demonstrates that photochemical reactions in conjugated polymers can be monitored by fluorescence spectroscopy down to the level of a few atoms, constituting an unprecedented degree of materials characterization.

Light-emitting diodes exhibiting efficient pure-white-light electroluminescence have been successfully developed by using a single polymer: polyfluorene derivatives with 1,8-naphthalimide chromophores chemically doped onto the polyfluorene backbones. By adjusting the emission wavelength of the 1,8-naphthalimide components and optimizing the relative content of 1,8-naphthalimide derivatives in the resulting polymers, white-light electroluminescence from a single polymer, as opposed to a polymer blend, has been obtained in a device with a configuration of indium tin oxide/poly(3,4-ethyleiledioxythiophene)(50 nm)/polymer(80 nm)/Ca(10 nm)/Al(100 nm). The device exhibits Commission Internationale de I'Eclairage coordinates of (0.32,0.36), a maximum brightness of 11900 cd m(-2), a current efficiency of 3.8 cd A(-1), a power efficiency of 2.0 lm W-1. an external quantum efficiency of 1.50 %, and quite stable color coordinates at different driving voltages, even at high luminances of over 5000 cd m(-2).

This account highlights recent progress towards understanding the complex hierarchical levels of solid-state structure in a prototypical helical hairy-rod polyfluorene, poly[9,9-bis(2-ethylhexyl)fluorene-2,7-diyl] (or PF2/6). This branched-side-chain containing polyfluorene undergoes a systematic intermolecular self-assembly and liquid-crystalline phase behavior in combination with uniaxial and biaxial alignment. The latter processes yield full three-dimensional orientation of the crystallites and polymer chains. Also reviewed are the impact of the molecular structure and phase behavior on surface morphology, anisotropic film formation, and, ultimately, the overall impact of these physical attributes on optical constants. This particular polyfluorene also represents a model system for demonstrating the applicability of mean-field theory in detailing the self-organization of aligned hairy-rod block-copolymer systems. These results of PF2/6 are compared to those of other archetypical -conjugated hairy-rod polymers. General guidelines of how molecular weight influences nanostructure, phase behavior, alignment, and surface morphology are given.

By using Ni0-mediated polymerization, we have systematically synthesized a series of fluorene-based copolymers composed of blue-, green-, and red-light-emitting comonomers with a view to producing polymers with white-light emission. 2,7-Dibromo-9,9-dihexylfluorene, {4-(2-[2,5-dibromo-4-{2-(4-diphenylamino-phenyl)-vinyl}-phenyl]-vinyl)-phenyl}-diphenylamine (DTPA), and 2-{2-(2-[4-{bis(4-bromo-phenyl)amino}-phenyl]-vinyl)-6-tert-butyl-pyran-4-ylidene}-malononitrile (TPDCM) were used as the blue-, green-, and red-light-emitting comonomers, respectively. It was found that the emission spectra of the resulting copolymers could easily be tuned by varying their DTPA and TPDCM content. Thus with the appropriate red/green/blue (RGB) unit ratio, we were able to obtain white-light emission from these copolymers. A white-light-emitting diode using the polyfluorene copolymer containing 3 % green-emitting DTPA and 2 % red-emitting TPDCM (PG3R2) with a structure of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid)/PG3R2/Ca/Al was found to exhibit a maximum brightness of 820 cd m–2 at 11 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.33,0.35), which are close to the standard CIE coordinates for white-light emission (0.33,0.33).