Energy Landscape of Vertically Anisotropic Polymer Blend Films toward Highly Efficient Polymer Light‐Emitting Diodes (PLEDs)

A blend of two hole‐dominant polymers is created and used as the light emissive layer in light‐emitting diodes to achieve high luminous efficiency up to 22 cd A^?1. The polymer blend F8_1?xSY_x is based on poly(9,9‐dioctylfluorene) (F8) and poly(para‐phenylene vinylene) derivative superyellow (SY). The blend system exhibits a preferential vertical concentration distribution. The resulting energy landscape modifies the overall charge transport behavior of the blend emissive layer. The large difference between the highest unoccupied molecular orbital levels of F8 (5.8 eV) and SY (5.3 eV) introduces hole traps at SY sites within the F8 polymer matrix. This slows down the hole mobility and facilitates a balance between the transport behavior of both the charge carriers. The balance due to such energy landscape facilitates efficient formation of excitons within the emission zone well away from the cathode and minimizes the surface quenching effects. By bringing the light‐emission zone in the middle of the F8_1?xSY_x film, the bulk of the film is exploited for the light emission. Due to the charge trapping nature of SY molecules in F8 matrix and pushing the emission zone in the center, the radiative recombination rate also increases, resulting in excellent device performance.     

Host Exciton Confinement for Enhanced Förster‐Transfer‐Blend Gain Media Yielding Highly Efficient Yellow‐Green Lasers

This paper reports state‐of‐the‐art fluorene‐based yellow‐green conjugated polymer blend gain media using Förster resonant‐energy‐transfer from novel blue‐emitting hosts to yield low threshold (≤7 kW cm^?2) lasers operating between 540 and 590 nm. For poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) (15 wt%) blended with the newly synthesized 3,6‐bis(2,7‐di([1,1′‐biphenyl]‐4‐yl)‐9‐phenyl‐9H‐fluoren‐9‐yl)‐9‐octyl‐9H–carbazole (DBPhFCz) a highly desirable more than four times increase (relative to F8BT) in net optical gain to 90 cm^?1 and 34 times reduction in amplified spontaneous emission threshold to 3 µJ cm^?2 is achieved. Detailed transient absorption studies confirm effective exciton confinement with consequent diffusion‐limited polaron‐pair generation for DBPhFCz. This delays formation of host photoinduced absorption long enough to enable build‐up of the spectrally overlapped, guest optical gain, and resolves a longstanding issue for conjugated polymer photonics. The comprehensive study further establishes that limiting host conjugation length is a key factor therein, with 9,9‐dialkylfluorene trimers also suitable hosts for F8BT but not pentamers, heptamers, or polymers. It is additionally demonstrated that the host highest occupied and lowest unoccupied molecular orbitals can be tuned independently from the guest gain properties. This provides the tantalizing prospect of enhanced electron and hole injection and transport without endangering efficient optical gain; a scenario of great interest for electrically pumped amplifiers and lasers.     

An Improved Optical Method for Determining the Order Parameter in Thin Oriented Molecular Films and Demonstration of a Highly Axial Dipole Moment for the Lowest Energy π–π* Optical Transition in Poly(9,9‐ dioctylfluorene‐co‐bithiophene)

Understanding the complex interplay between the 3D structural hierarchy within thin films of conjugated polymers and the properties of devices based thereon is starting to be recognized as an important challenge in the continued development of these materials for a range of applications. As a result, for example, accurate measurements of molecular orientation and elucidation of its influence on optical characteristics are of significant interest. Here we report an improved optical method to determine both the order parameter and the angle between the polymer backbone director and the optical transition dipole moment for the lowest energy π–π* absorption peak in uniaxially aligned thin films of conjugated polymers. The method uses a combination of polarized Raman spectroscopy and UV‐vis spectroscopy and is based on a general theoretical treatment to describe the expected Raman and optical absorption anisotropies of such films. It is applied to study the orientation within thermotropically aligned films of the electroluminescent fluorene‐based copolymer poly(9,9‐dioctylfluorene‐co‐bithiophene) (F8T2). A more highly axial transition dipole moment is found for the dominant long wavelength absorption peak of F8T2 compared to that of other fluorene‐based (co)polymers. The angle between the polymer backbone director and the transition dipole is estimated to be β ≤ 3°, a deduction that helps to explain the relatively large optical dichroism for aligned films of F8T2 and that offers the prospect of highly polarized electroluminescence from F8T2‐based light‐emitting diodes.     

Suppression of the Keto‐Emission in Polyfluorene Light‐Emitting Diodes: Experiments and Models

The spectral characteristics of polyfluorene (PF)‐based light‐emitting diodes (LEDs) containing a defined low concentration of either keto‐defects or of the polymer poly(9,9‐octylfluorene‐co‐benzothiadiazole) (F8BT) are presented. Both types of blend layers were tested in different device configurations with respect to the relative and absolute intensities of green and blue emission components. It is shown that blending hole‐transporting molecules into the emission layer at low concentration or incorporation of a suitable hole‐transporting layer reduces the green emission contribution in the electroluminescence (EL) spectrum of the PF:F8BT blend, which is similar to what is observed for the keto‐containing PF layer. We conclude that the keto‐defects in PF homopolymer layers mainly constitute weakly emissive electron traps, in agreement with the results of quantum‐mechanical calculations.     

n‐Doping of a Low‐Electron‐Affinity Polymer Used as an Electron‐Transport Layer in Organic Light‐Emitting Diodes

n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]₂. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]₂, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]₂‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Stable Blue Emission from a Polyfluorene/Layered‐Compound Guest/Host Nanocomposite

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 π–π 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.     

Conjugated Polymers: High‐Resolution Scanning Near‐Field Optical Lithography of Conjugated Polymers (Adv. Funct. Mater. 17/2010)

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 (< λ/5) is demonstrated over areas up to 20 μm × 20 μm. 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.     

Charge‐Carrier Balance and Color Purity in Polyfluorene Polymer Blends for Blue Light‐Emitting Diodes

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.     

Electron‐Enhanced Hole Injection in Blue Polyfluorene‐Based Polymer Light‐Emitting Diodes

It has recently been reported that, after electrical conditioning, an ohmic hole contact is formed in poly(9,9‐dioctylfluorene) (PFO)‐based polymer light‐emitting diodes (PLED), despite the large hole‐injection barrier obtained with a poly(styrene sulfonic acid)‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT:PSS) anode. We demonstrate that the initial current at low voltages in a PEDOT:PSS/PFO‐based PLED is electron dominated. The voltage at which the hole injection is enhanced strongly depends on the electron‐transport properties of the device, which can be modified by the replacement of reactive end groups by monomers in the synthesis. Our measurements reveal that the switching voltage of the PLED is governed by the electron concentration at the PEDOT:PSS/PFO contact. The switching effect in PFO is only observed for a PEDOT:PSS hole contact and not for other anodes such as indium tin oxide or Ag.     

Optically‐Pumped Lasing in Hybrid Organic–Inorganic Light‐Emitting Diodes

Here, the use of metal oxide layers both for charge transport and injection into an emissive semiconducting polymer and also for the control of the in‐plane waveguided optical modes in light‐emitting diodes (LEDs) is reported. The high refractive index of zinc oxide is used to confine these modes away from the absorbing electrodes, and include a nano‐imprinted grating in the polymer layer to introduce distributed feedback and enhance optical out‐coupling. These structures show a large increase in the luminescence efficiency over conventional devices, with photoluminescence efficiency increased by up to 45%. Furthermore, optically‐pumped lasing in hybrid oxide polymer LEDs is demonstrated. A tuneable lasing emission is also obtained in a single device structure by employing a graduated thickness of a zinc oxide inter‐layer. This demonstrates the scope for using such architectures to improve the external efficiency of organic semiconductor LEDs, and opens new possibilities for the realization of polymer injection lasers.     

High‐Resolution Scanning Near‐Field Optical Lithography of Conjugated Polymers

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 (< λ/5) is demonstrated over areas up to 20 μm × 20 μm. 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.     

Correlating Emissive Non‐Geminate Charge Recombination with Photocurrent Generation Efficiency in Polymer/Perylene Diimide Organic Photovoltaic Blend Films

Evidence for a correlation between the dynamics of emissive non‐geminate charge recombination within organic photovoltaic (OPV) blend films and the photocurrent generation efficiency of the corresponding blend‐based solar cells is presented. Two model OPV systems that consist of binary blends of electron acceptor N′‐bis(1‐ethylpropyl)‐3,4,9,10‐perylene tetracarboxy diimide (PDI) with either poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) or poly(9,9‐dioctylindenofluorene‐co‐benzothiadiazole) (PIF8BT) as electron donor are studied. For the F8BT:PDI and PIF8BT:PDI devices photocurrent generation efficiency is shown to be related to the PDI crystallinity. In contrast to the F8BT:PDI system, thermal annealing of the PIF8BT:PDI layer at 90 °C has a positive impact on the photocurrent generation efficiency and yields a corresponding increase in PL quenching. The devices of both blends have a strongly reduced photocurrent on higher temperature annealing at 120 °C. Delayed luminescence spectroscopy suggests that the improved efficiency of photocurrent generation for the 90 °C annealed PIF8BT:PDI layer is a result of optimized transport of the photogenerated charge‐carriers as well as of enhanced PL quenching due to the maintenance of optimized polymer/PDI interfaces. The studies propose that charge transport in the blend films can be indirectly monitored from the recombination dynamics of free carriers that cause the delayed luminescence. For the F8BT:PDI and PIF8BT:PDI blend films these dynamics are best described by a power‐law decay function and are found to be temperature dependent.     

Formation of a Ground‐State Charge‐Transfer Complex in Polyfluorene//[6,6]‐Phenyl‐C61 Butyric Acid Methyl Ester (PCBM) Blend Films and Its Role in the Function of Polymer/PCBM Solar Cells

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.     

Photophysics and Photocurrent Generation in Polythiophene/Polyfluorene Copolymer Blends

Here, studies on the evolution of photophysics and device performance with annealing of blends of poly(3‐hexylthiophene) with the two polyfluorene copolymers poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2′′‐diyl) (F8TBT) and poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) are reported. In blends with F8TBT, P3HT is found to reorganize at low annealing temperatures (100 °C or below), evidenced by a redshift of both absorption and photoluminescence (PL), and by a decrease in PL lifetime. Annealing to 140 °C, however, is found to optimize device performance, accompanied by an increase in PL efficiency and lifetime. Grazing‐incidence small‐angle X‐ray scattering is also performed to study the evolution in film nanomorphology with annealing, with the 140 °C‐annealed film showing enhanced phase separation. It is concluded that reorganization of P3HT alone is not sufficient to optimize device performance but must also be accompanied by a coarsening of the morphology to promote charge separation. The shape of the photocurrent action spectra of P3HT:F8TBT devices is also studied, aided by optical modeling of the absorption spectrum of the blend in a device structure. Changes in the shape of the photocurrent action spectra with annealing are observed, and these are attributed to changes in the relative contribution of each polymer to photocurrent as morphology and polymer conformation evolve. In particular, in as‐spun films from xylene, photocurrent is preferentially generated from ordered P3HT segments attributed to the increased charge separation efficiency in ordered P3HT compared to disordered P3HT. For optimized devices, photocurrent is efficiently generated from both P3HT and F8TBT. In contrast to blends with F8TBT, P3HT is only found to reorganize in blends with F8BT at annealing temperatures of over 200 °C. The low efficiency of the P3HT:F8BT system can then be attributed to poor charge generation and separation efficiencies that result from the failure of P3HT to reorganize.     

End‐Capping as a Method for Improving Carrier Injection in Electrophosphorescent Light‐Emitting Diodes

The electronic properties, carrier injection, and transport into poly(9,9‐dioctylfluorene) (PFO), PFO end‐capped with hole‐transporting moieties (HTM), PFO–HTM, and PFO end‐capped with electron‐transporting moieties (ETM), PFO–ETM, were investigated. The data demonstrate that charge injection and transport can be tuned by end‐capping with HTM and ETM, without significantly altering the electronic properties of the conjugated backbone. End‐capping with ETM resulted in more closely balanced charge injection and transport. Single‐layer electrophosphorescent light‐emitting diodes (LEDs), fabricated from PFO, PFO–HTM and PFO–ETM as hosts and tris[2,5‐bis‐2′‐(9′,9′‐dihexylfluorene)pyridine‐κ²NC_3′]iridium(III ), Ir(HFP)₃ as the guest, emitted red light with brightnesses of 2040 cd m^–2, 1940 cd m^–2 and 2490 cd m^–2 at 290 mA cm^–2 (16 V) and with luminance efficiencies of 1.4 cd A^–1, 1.4 cd A^–1 and 1.8 cd A^–1 at 4.5 mA cm^–2 for PFO, PFO–HTM, and PFO–ETM, respectively.     

Local Probing of Photocurrent and Photoluminescence in a Phase‐Separated Conjugated‐Polymer Blend by Means of Near‐Field Excitation

In this paper scanning near‐field microscopy is used to characterize polymer blends for photovoltaic applications, and fluorescence imaging and photoconductivity are combined to elucidate the spatial distribution and relative efficiency of current generation and photoluminescence in different domains of compositionally heterogeneous films. Focus is placed on a binary system consisting of poly[(9,9‐dioctylfluorene)‐alt‐benzothiadiazole] (F8BT) and poly[(9,9‐dioctylfluorene)‐alt‐(bis(N,N′‐(4‐butylphenyl))‐bis(N,N′‐phenyl‐1,4‐phenylenediamine))] (PFB), spun from xylene solutions, so as to obtain phase separation on micrometer and nanometer length scales. Protruding regions with diameters of about 5 μm in the topography image coincide with regions of high photocurrent (PC) and luminescence; these regions are identified as being F8BT‐rich. A general method to estimate the photoluminescence efficiency in the different domains of phase‐separated blends is proposed. As expected, lack of enhancement of the PC signal at the boundaries between protruding and lower‐lying phases indicate that these microscale boundaries play a small role in the charge generation by exciton splitting. This is consistent with the domains compositional inhomogeneity, and thus with finer phase separation within the domains. We also provide an analysis of the extent to which the metallized probe perturbs the near‐field photocurrent signal by integrating Poisson's equation. Finally, by using a Bethe–Bouwkamp model, the energy absorbed by the polymer film in the different regions is estimated.     

The Effect of Ketone Defects on the Charge Transport and Charge Recombination in Polyfluorenes

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.     

Improved Performance of Polymer:Polymer Solar Cells by Doping Electron‐Accepting Polymers with an Organosulfonic Acid

The performance of polymer:polymer solar cells that are made using blend films of poly(3‐hexylthiophene) (P3HT) and poly(9,9‐dioctylfluorene‐co‐ benzothiadiazole (F8BT) is improved by doping the F8BT polymer with an organosulfonic acid [4‐ethylbezenesulfonic acid (EBSA)]. The EBSA doping of F8BT, to form F8BT‐EBSA, is performed by means of a two‐stage reaction at room temperature and 60°C with various EBSA weight ratios. The X‐ray photoelectron spectroscopy measurement reveals that both sulfur and nitrogen atoms in the F8BT polymer are affected by the EBSA doping. The F8BT‐EBSA films exhibit huge photoluminescence quenching, ionization potential shift toward lower energy, and greatly enhanced electron mobility. The short‐circuit current density of solar cells is improved by ca. twofold (10 wt.% EBSA doping), while the open‐circuit voltage increases by ca. 0.4 V. Consequently, the power conversion efficiency was improved by ca. threefold, even though the optical density of the P3HT:F8BT‐EBSA blend film is reduced by 10 wt.% EBSA doping due to the nanostructure and surface morphology change.     

Eleven‐Membered Fused‐Ring Low Band‐Gap Polymer with Enhanced Charge Carrier Mobility and Photovoltaic Performance

A multi‐ring, ladder‐type low band‐gap polymer (PIDTCPDT‐DFBT) is developed to show enhanced light harvesting, charge transport, and photovoltaic performance. It possesses excellent planarity and enhanced effective conjugation length compared to the previously reported fused‐ring polymers. In order to understand the effect of extended fused‐ring on the electronic and optical properties of this polymer, a partially fused polymer PIDTT‐T‐DFBT is also synthesized for comparison. The fully rigidified polymer provides lower reorganizational energy, resulting in one order higher hole mobility than the reference polymer. The device made from PIDTCPDT‐DFBT also shows a quite promising power conversion efficiency of 6.46%. Its short‐circuit current (14.59 mA cm^?2) is also among the highest reported for ladder‐type polymers. These results show that extending conjugation length in fused‐ring ladder polymers is an effective way to reduce band‐gap and improve charge transport for efficient photovoltaic devices.