Distannylated Bithiophene Imide: Enabling High‐Performance n‐Type Polymer Semiconductors with an Acceptor–Acceptor Backbone

A distannylated electron‐deficient bithiophene imide (BTI‐Tin) monomer was synthesized and polymerized with imide‐functionalized co‐units to afford homopolymer PBTI and copolymer P(BTI‐BTI2), both featuring an acceptor–acceptor backbone with high molecular weight. Both polymers exhibited excellent unipolar n‐type character in transistors with electron mobility up to 2.60 cm² V^?1 s^?1. When applied as acceptor materials in all‐polymer solar cells, PBTI and P(BTI‐BTI2) achieved high power‐conversion efficiency (PCE) of 6.67 % and 8.61 %, respectively. The PCE (6.67 %) of polymer PBTI, synthesized from the distannylated monomer, is much higher than that (0.14 %) of the same polymer PBTI*, synthesized from typical dibrominated monomer. The 8.61 % PCE of copolymer P(BTI‐BTI2) is also higher than those (<1 %) of homopolymers synthesized from dibrominated monomers. The results demonstrate the success of BTI‐Tin for accessing n‐type polymers with greatly improved device performance.     

A Unique Blend of 2‐Fluorenyl‐2‐anthracene and 2‐Anthryl‐2‐anthracence Showing White Emission and High Charge Mobility

White‐light‐emitting materials with high mobility are necessary for organic white‐light‐emitting transistors, which can be used for self‐driven OLED displays or OLED lighting. In this study, we combined two materials with similar structures—2‐fluorenyl‐2‐anthracene (FlAnt) with blue emission and 2‐anthryl‐2‐anthracence (2A) with greenish‐yellow emission—to fabricate OLED devices, which showed unusual solid‐state white‐light emission with the CIE coordinates (0.33, 0.34) at 10 V. The similar crystal structures ensured that the OTFTs based on mixed FlAnt and 2A showed high mobility of 1.56 cm² V⁻¹ s⁻¹. This simple method provides new insight into the design of high‐performance white‐emitting transistor materials and structures.     

Constructing a Strongly Absorbing Low‐Bandgap Polymer Acceptor for High‐Performance All‐Polymer Solar Cells

All‐polymer solar cells (all‐PSCs) offer unique morphology stability for the application as flexible devices, but the lack of high‐performance polymer acceptors limits their power conversion efficiency (PCE) to a value lower than those of the PSCs based on fullerene derivative or organic small molecule acceptors. We herein demonstrate a strategy to synthesize a high‐performance polymer acceptor PZ1 by embedding an acceptor–donor–acceptor building block into the polymer main chain. PZ1 possesses broad absorption with a low band gap of 1.55 eV and high absorption coefficient (1.3×10⁵ cm⁻¹). The all‐PSCs with the wide‐band‐gap polymer PBDB‐T as donor and PZ1 as acceptor showed a record‐high PCE of 9.19 % for the all‐PSCs. The success of our polymerization strategy can provide a new way to develop efficient polymer acceptors for all‐PSCs.     

Synthesis and characterization of porphyrin‐based D‐π‐A conjugated polymers for polymer solar cells

Two novel porphyrin‐based D‐A conjugated copolymers, PFTTQP and PBDTTTQP , consisting of accepting quinoxalino[2,3‐b′]porphyrin unit and donating fluorene or benzo[1,2‐b:4,5‐b′]dithiophene unit, were synthesized, respectively via a Pd‐catalyzed Stille‐coupling method. The quinoxalino[2,3‐b′]porphyrin, an edge‐fused porphyrin monomer, was used as a building block of D‐A copolymers, rather than the simple porphyrin unit in conventional porphyrin‐based photovoltaic polymers reported in literature, to enhance the coplanarity and to extend the π‐conjugated system of polymer main chains, and consequently to facilitate the intramolecular charge transfer (ICT). The thermal stability, optical, and electrochemical properties as well as the photovoltaic characteristics of the two polymers were systematically investigated. Both the polymers showed high hole mobility, reaching 4.3 × 10^?4 cm² V^?1 s^?1 for PFTTQP and 2.0 × 10^?4 cm² V^?1 s^?1 for PBDTTTQP . Polymer solar cells (PSCs) made from PFTTQP and PBDTTTQP demonstrated power conversion efficiencies (PCEs) of 2.39% and 1.53%, both of which are among the highest PCE values in the PSCs based on porphyrin‐based conjugated polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Novel Donor–Acceptor Polymer Containing 4,7‐Bis(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole for Polymer Solar Cells with Power Conversion Efficiency of 6.21%

In order to improve the solution processability of 4,7‐bis(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (DTBT)‐based polymers, novel donor–acceptor polymer PTOBDTDTBT containing DTBT and benzo[1,2‐b:4,5‐b′]dithiophene (BDT) with conjugated side chain is designed and synthesized with narrow band gap 1.67 eV and low lying HOMO energy level −5.4 eV. The blend film of PTOBDTDTBT and PC₇₁BM exhibits uniform and smooth film with root‐mean‐square (RMS) surface roughness 1.15 nm because of the excellent solubility of PTOBDTDTBT when six octyloxy side chains are introduced. The hole mobility of the blend film is measured to be 4.4 × 10⁻⁵ cm² V⁻¹s⁻¹ by the space‐charge‐limited current (SCLC) model. The optimized polymer solar cells (PSCs) based on PTOBDTDTBT /PC₇₁BM exhibits an improved PCE of 6.21% with V_oc = 0.80 V, J_sc = 11.94 mA cm⁻² and FF = 65.10%, one of the highest PCE in DTBT containing polymers.

     

4,5,9,10‐Pyrene Diimides: A Family of Aromatic Diimides Exhibiting High Electron Mobility and Two‐Photon Excited Emission

The design and synthesis of high‐performance n‐type organic semiconductors are important for the development of future organic optoelectronics. Facile synthetic routes to reach the K‐region of pyrene and produce 4,5,9,10‐pyrene diimide (PyDI) derivatives are reported. The PyDI derivatives exhibited efficient electron transport properties, with the highest electron mobility of up to 3.08 cm² V⁻¹ s⁻¹. The tert‐butyl‐substituted compounds (t‐PyDI) also showed good one‐ and two‐photon excited fluorescence properties. The PyDI derivatives are a new family of aromatic diimides that may exhibit both high electron mobility and good light‐emitting properties, thus making them excellent candidates for future optoelectronics.     

High‐Efficiency Large‐Bandgap Material for Polymer Solar Cells

High‐molecular‐weight conjugated polymer HD‐PDFC‐DTBT with N‐(2‐hexyldecyl)‐3,6‐difluorocarbazole as the donor unit, 5,6‐bis(octyloxy)benzothiadiazole as the acceptor unit, and thiophene as the spacer is synthesized by Suzuki polycondensation. HD‐PDFC‐DTBT shows a large bandgap of 1.96 eV and a high hole mobility of 0.16 cm² V⁻¹ s⁻¹. HD‐PDFC‐DTBT:PC₇₁BM‐based inverted polymer solar cells (PSCs) give a power conversion efficiency (PCE) of 7.39% with a V_oc of 0.93 V, a J_sc of 14.11 mA cm⁻², and an FF of 0.56.

     

Low‐Voltage All‐Polymer Field‐Effect Transistor Fabricated Using an Inkjet Printing Technique

Summary: An all‐polymer field‐effect transistor (FET) fabricated using an inkjet printing technique is presented in this paper. Poly(3,4‐ethylenedioxythiophene) works as the source/drain/gate electrode material because of its good conductivity. Polypyrrole acts as the semiconducting layer. Poly(vinyl pyrrolidone) K60, an insulating polymer with a dielectric constant of 60, operates as the dielectric layer. All the polymers are diluted with deionized water, and can be printed with a piezoelectric inkjet printing system. The device functions at a depletion mode with low operation voltage. It has a field‐effect mobility of 0.1 cm² · V⁻¹ · s⁻¹, an on/off ratio of 2.9 × 10³, and a subthreshold slope of 2.81 V · decade⁻¹.

Schematic of the all‐polymer FET synthesized here.     

Dithienylmethanone‐Based Cross‐Conjugated Polymer Semiconductors: Synthesis,Characterization, and Application in Field‐Effect Transistors

Herein, we report the synthesis, characterization, and field‐effect properties of two cross‐conjugated dithienylmethanone (DMO)‐based alternating polymers, namely, PDMO‐S and PDMO‐Se . Both polymers possess high thermal stability, good solubility, and broad absorption spectra. Their electrochemical properties were investigated using cyclic voltammetry, indicating that PDMO‐Se has higher HOMO/LUMO energy levels of −5.49/−3.49 eV than −5.57/−3.58 eV of PDMO‐S . The two polymers exhibited promising charge transport properties with the highest hole mobility of 0.12 cm² V⁻¹ s⁻¹ for PDMO‐S and 0.025 cm² V⁻¹ s⁻¹ for PDMO‐Se . AFM and 2D‐GIXRD analyses demonstrated that the PDMO‐S formed lamellar, edge‐on packing thin film with close π‐π stacking. These findings suggest that cross‐conjugated polymers might be potential semiconducting materials for low‐cost and flexible organic electronics. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1012–1019     

Coordination Polymer Framework Based On‐Chip Micro‐Supercapacitors with AC Line‐Filtering Performance

On‐chip micro‐supercapacitors (MSCs) are important Si‐compatible power‐source backups for miniaturized electronics. Despite their tremendous advantages, current on‐chip MSCs require harsh processing conditions and typically perform like resistors when filtering ripples from alternating current (AC). Herein, we demonstrated a facile layer‐by‐layer method towards on‐chip MSCs based on an azulene‐bridged coordination polymer framework (PiCBA). Owing to the good carrier mobility (5×10⁻³ cm² V⁻¹ s⁻¹) of PiCBA, the permanent dipole moment of azulene skeleton, and ultralow band gap of PiCBA, the fabricated MSCs delivered high specific capacitances of up to 34.1 F cm⁻³ at 50 mV s⁻¹ and a high volumetric power density of 1323 W cm⁻³. Most importantly, such MCSs exhibited AC line‐filtering performance (−73° at 120 Hz) with a short resistance–capacitance constant of circa 0.83 ms.     

Conjugated polymers based on 1,8‐naphthalene monoimide with high electron mobility

1,4,8,9‐Naphthalene diimides (NDIs) with strong electron accepting ability and high stability are excellent building blocks for semiconductor polymers. However, 1,8‐naphthalene monoimide (NMI) with similar structure and energy levels as that of NDI has never been used to construct conjugated polymers because of synthetic difficulty. Herein, 3,6‐dibromo‐NMI (DBNMI) with bulky alkyl groups was obtained effectively in a four‐step synthesis, and three donor‐acceptor (D‐A) type conjugated polymers based on NMI were firstly prepared. These polymers have strong absorption in the range of 300–600 nm, low LUMO level of 3.68 eV, and moderate bandgaps of 2.18 eV. Space charge limiting current measurements indicate these polymers are typical electron transporting materials, and the highest electron mobility is up to 5.8 × 10⁻³ cm² V⁻¹ s⁻¹, which is close to the star acceptor based on NDI (N2200, 5.0 × 10⁻³ cm² V⁻¹ s⁻¹). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 276–281     

Diketopyrrolopyrrole‐Porphyrin Based Conjugated Polymers for Ambipolar Field‐Effect Transistors

Porphyrin‐based molecules have been widely used in dye‐sensitized solar cells and bulk heterojunction solar cells, but their application in field‐effect transistors (FETs) is limited. In this work, two conjugated polymers based on diketopyrrolopyrrole and porphyrin units were developed for FETs. The polymers exhibit extra‐low band gap with energy levels close to −4.0 eV and −5.0 eV due to the strong electron‐donating and withdrawing ability of porphyrin and diketopyrrolopyrrole. With additionally high crystalline properties, ambipolar charge carrier transports with a hole mobility of 0.1 cm² V⁻¹ s⁻¹ in FETs were realized in these polymers, representing the highest performance in solution‐processed FETs based on porphyrin unit.     

High‐performance field‐effect transistors based on furan‐containing diketopyrrolopyrrole copolymer under a mild annealing temperature

Two furan‐flanked polymers poly{3,6‐difuran‐2‐yl‐2,5‐di(2‐octyldodecyl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐alt‐thienylenevinylene} (PDVFs), with a highly π‐extended diketopyrrolopyrrole backbone, are developed for solution‐processed high‐performance polymer field‐effect transistors (FETs). Atomic force microscopy and grazing incidence X‐ray scattering analyses indicate that PDVF‐8 and PDVF‐10 films exhibit a similar nodular morphology with the ultrasmall lamellar distances of 16.84 and 18.98 Å, respectively. When compared with the reported polymers with the same alkyl substitutes, this is the smallest d‐spacing value observed to date. This closed lamellar crystallinity facilitates charge carrier transport. Therefore, polymer thin‐film transistors fabricated from as‐spun PDVF‐8 films exhibit a high hole mobility exceeding 1.0 cm² V^?1 s^?1 with a current on/off ratio above 10⁶. After annealing treatment at 100 °C in air, the highest hole mobility of PDVF‐8‐based FETs was significantly improved to 1.90 cm² V^?1 s^?1, which is among the highest values of the reported FET devices fabricated from polymer thin films based on this mild annealing temperature. In contrast, long alkyl‐substituted PDVF‐10 exhibited a relatively low hole mobility of 1.65 cm² V^?1 s^?1 mainly resulting from low molecular weight. This work demonstrated that PDVFs would be promising semiconductors for developing cost‐effective and large‐scale production of flexible organic electronics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1970–1977     

Significant Difference in Semiconducting Properties of Isomeric All‐Acceptor Polymers Synthesized via Direct Arylation Polycondensation

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon‐hydrogen (C‐H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high‐molecular‐weight all‐acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co‐catalysts. We thus obtained two isomeric all‐acceptor polymers, P1 and P2, which have the same backbone and side‐chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing, and charge‐transport properties. P2 with a greater backbone torsion has favorable edge‐on orientations and a high electron mobility μ_e of 2.55 cm² V^?1 s^?1. Moreover, P2‐based transistors show an excellent shelf‐storage stability in air even after the storage for 1 month.     

3,4‐Phenylenedioxythiophene (PheDOT) Based Hole‐Transporting Materials for Perovskite Solar Cells

Two new electron‐rich molecules based on 3,4‐phenylenedioxythiophene (PheDOT) were synthesized and successfully adopted as hole‐transporting materials (HTMs) in perovskite solar cells (PSCs). X‐ray diffraction, absorption spectra, photoluminescence spectra, electrochemical properties, thermal stabilities, hole mobilities, conductivities, and photovoltaic parameters of PSCs based on these two HTMs were compared with each other. By introducing methoxy substituents into the main skeleton, the energy levels of PheDOT‐core HTM were tuned to match with the perovskite, and its hole mobility was also improved (1.33×10^?4 cm² V^?1 s^?1, being higher than that of spiro‐OMeTAD, 2.34×10^?5 cm² V^?1 s^?1). The PSC based on MeO‐PheDOT as HTM exhibits a short‐circuit current density (J_sc) of 18.31 mA cm^?2, an open‐circuit potential (V_oc) of 0.914 V, and a fill factor (FF) of 0.636, yielding an encouraging power conversion efficiency (PCE) of 10.64 % under AM 1.5G illumination. These results give some insight into how the molecular structures of HTMs affect their performances and pave the way for developing high‐efficiency and low‐cost HTMs for PSCs.     

Novel Conjugated Polymers Based on Dithieno[3,2‐b:6,7‐b]carbazole for Solution Processed Thin‐Film Transistors

Two conjugated polymers (CPs) P‐tCzC12 and P‐tCzC16 comprising alternating dithieno[3,2‐b:6,7‐b]carbazole and 4,4′‐dihexadecyl‐2,2′‐bithiophene units have been designed and synthesized. Upon thermal annealing, they can form ordered thin films in which the polymer backbones dominantly adopted an edge‐on orientation respective to the substrate with a lamellar spacing of ≈24 Å and a π‐stacking distance of ≈3.7 Å. Organic thin‐film transistors (OTFTs) were fabricated by solution casting. A hole mobility of 0.39 cm² V⁻¹s⁻¹ has been demonstrated with P‐tCzC16. This value is the highest among the CPs containing heteroacenes larger than 4 rings.     

Silaindacenodithiophene‐Based Fused‐Ring Non‐Fullerene Electron Acceptor for Efficient Polymer Solar Cells

In this work, a new A‐D‐A type nonfullerene small molecular acceptor SiIDT‐IC, with a fused‐ring silaindacenodithiophene (SiIDT) as D unit and 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene)malononitrile (INCN) as the end A unit, was design and synthesized. The SiIDT‐IC film shows absorption peak and edge at 695 and 733 nm, respectively. The HOMO and LUMO of SiIDT‐IC are of −5.47 and −3.78 eV, respectively. Compared with carbon‐bridging, the Si‐bridging can result in an upper‐lying LUMO level of an acceptor, which is benefit to achieve a higher open‐circuit voltage in polymer solar cells (PSCs). Complementary absorption and suitable energy level alignment between SiIDT‐IC and wide bandgap polymer donor PBDB‐T were found. For the PBDB‐T:SiIDT‐IC based inverted PSCs, a D/A ratio of 1: 1 was optimal to achieve a power conversion efficiency (PCE) of 7.27%. With thermal annealing (TA) of the blend film, a higher PCE of 8.16% could be realized due to increasing of both short‐circuit current density and fill factor. After the TA treatment, hole and electron mobilities were elevated to 3.42 × 10⁻⁴ and 1.02 × 10⁻⁴ cm²·V⁻¹·s⁻¹, respectively. The results suggest that the SiIDT, a Si‐bridged fused ring, is a valuable D unit to construct efficient nonfullerene acceptors for PSCs.     

Molecular engineering of conjugated polymers for solar cells and field‐effect transistors: Side‐chain versus main‐chain electron acceptors

Two model polymers, containing fluorene as an electron‐donating moiety and benzothiadiazole (BT) as an electron‐accepting moiety, have been synthesized by Suzuki coupling reaction. Both polymers are composed of the same chemical composition, but the BT acceptor can be either at a side‐chain (i.e., S‐polymer) or along the polymer main chain (i.e., M‐polymer). Their optical, electrochemical, and photovoltaic properties, together with the field‐effect transistor (FET) characteristics, have been investigated experimentally and theoretically. The FET carrier mobilities were estimated to be 5.20 × 10^?5 and 3.12 × 10^?4 cm² V^?1 s^?1 for the S‐polymer and M‐polymer, respectively. Furthermore, polymeric solar cells (PSCs) with the ITO/PEDOT:PSS/S‐polymer or M‐polymer:PC₇₁BM(1:4)/Al structure were constructed and demonstrated to show a power conversion efficiency of 0.82 and 1.24% for the S‐polymer and M‐polymer, respectively. The observed superior device performances for the M‐polymer in both FET and PSCs are attributable to its relatively low band‐gap and close molecular packing for efficient solar light harvesting and charge transport. This study provides important insights into the design of ideal structure–property relationships for conjugate polymers in FETs and PSCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

P4VP and oligo(phenylenevinylene)‐perylenebisimide mixed donor‐acceptor supramolecular comb polymer complexes with improved charge carrier mobility

Random donor‐acceptor (D‐A) supramolecular comb polymers were formed when hydroxyl functionalized donor and acceptor small molecules based on Oligo(phenylenevinylene) (named OPVCN‐OH ) and Perylenebisimide (named UPBI‐PDP ), respectively, were complexed with Poly(4‐vinyl pyridine) (P4VP). A series of random D‐A supramolecular comb polymers were formed by varying the ratios of UPBI‐PDP and OPVCN‐OH with P4VP. A 100% P4VP‐donor polymer complex [ P4VP(OPV_1.00 )] and a 100% P4VP‐acceptor polymer complex [ P4VP(UPBI_1.00 )] were also synthesized and characterized. Complex formation was confirmed by FT‐IR and ¹H NMR spectroscopy. Solid state structural studies carried out using small angle X‐ray scattering and wide angle X‐ray diffraction experiments revealed altered packing of the D and A molecules in the complexes. Transmission electron microscopy images showed lamellar structures in the < 10 nm scale for the P4VP(OPV_1.00 ), P4VP(UPBI_1.00 ), and mixed P4VP (D‐A) complexes. The effect of the nanoscopic D‐A self‐assembly on the bulk mobility of the materials was probed using SCLC measurements. The mixed D‐A random complexes exhibited ambipolar charge transport characteristics with higher values for the average bulk hole mobility estimate. P4VP(OPV_0.25 + UPBI_0.75) exhibited an average hole mobility in the order of 10^?2cm² V^?1 s^?1 and electron mobility 10^?5cm² V^?1 s^?1. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2403–2412     

Trichalcogenasumanene ortho‐Quinones: Synthesis,Properties, and Transformation into Various Heteropolycycles

The regioselective transformation of heterobuckybowl trichalcogenasumanenes 1 a , b at peripheral butoxy groups afforded trichalcogenasumanene ortho ‐quinones 2 a , b . Compounds 2 a , b are distinct from 1 a , b in terms of their molecular geometry and electronic state; that is, they have a shallower bowl depth and show absorbance in the NIR region. The reaction of 2 a , b with diamines resulted in a variety of heteropolycycles, including molecular spoon 3 a – 6 a , planar π‐systems 3 b – 6 b , and highly twisted [7‐6‐6]‐fused systems 7 a , b . These new heteropolycycles had different optical/electrical properties: 4 a,b showed hole mobility of approximately 0.002 cm² V⁻¹ s⁻¹, 6 a displayed red emission in both solution and the solid state, and 7 a , b formed tight stacks of the curved π‐surface.