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.     

A Pentacyclic Nitrogen‐Bridged Thienyl–Phenylene–Thienyl Arene for Donor–Acceptor Copolymers: Synthesis,Characterization, and Applications in Field‐Effect Transistors and Polymer Solar Cells

A pentacyclic benzodipyrrolothiophene ( BDPT ) unit, in which two outer thiophene rings are covalently fastened with the central phenylene ring by nitrogen bridges, was synthesized. The two pyrrole units embedded in BDPT were constructed by using one‐pot palladium‐catalyzed amination. The coplanar stannylated Sn‐BDPT building block was copolymerized with electron‐deficient thieno[3,4‐c]pyrrole‐4,6‐dione ( TPD ), benzothiadiazole ( BT ), and dithienyl‐diketopyrrolopyrrole ( DPP ) acceptors by Stille polymerization. The bridging nitrogen atoms make the BDPT motif highly electron‐abundant and structurally coplanar, which allows for tailoring the optical and electronic properties of the resultant polymers. Strong photoinduced charge‐transfer with significant band‐broadening in the solid state and relatively higher oxidation potential are characteristic of the BDPT‐based polymers. Poly(benzodipyrrolothiophene‐alt‐benzothiadiazole) ( PBDPTBT ) achieved the highest field‐effect hole mobility of up to 0.02 cm² V^?1 s^?1. The photovoltaic device using the PBDPTBT /PC₇₁BM blend (1:3, w/w) exhibited a V_oc of 0.6 V, a J_sc of 10.34 mA cm^?2, and a FF of 50 %, leading to a decent PCE of 3.08 %. Encouragingly, the device incorporating poly(benzodipyrrolothiophene‐alt‐thienopyrrolodione) ( PBDPTTPD )/PC₇₁BM (1:3, w/w) composite delivered a highest PCE of 3.72 %. The enhanced performance arises from the lower‐lying HOMO value of PBDPTTPD to yield a higher V_oc of 0.72 V.     

Alternating and Diblock Donor–Acceptor Conjugated Polymers Based on Diindeno[1,2‐b:2′,1′‐d]thiophene Structure: Synthesis,Characterization, and Photovoltaic Applications

Pentacyclic diindeno[1,2‐b:2′,1′‐d]thiophene ( DIDT ) unit is a rigid and coplanar conjugated molecule. To the best of our knowledge, this attractive molecule has never been incorporated into a polymer and thus its application in polymer solar cells has never been explored. For the first time, we report the detailed synthesis of the tetra‐alkylated DIDT molecule leading to its dibromo‐ and diboronic ester derivatives, which are the key monomers for preparation of DIDT ‐based polymers. Two donor–acceptor alternating polymers, poly(diindenothiophene‐alt‐benzothiadiazole) PDIDTBT and poly(diindenothiophene‐alt‐dithienylbenzothiadiazole) PDIDTDTBT , were synthesized by using Suzuki polymerization. Copolymer PTDIDTTBT was also prepared by using Stille polymerization. Although PTDIDTTBT is prepared through a manner of random polymerization, we found that the different reactivities of the dibromo‐monomers lead to the resulting polymer having a block copolymer arrangement. With the higher structural regularity, PTDIDTTBT , symbolized as (thiophene‐alt‐ DIDT )_0.5‐block‐(thiophene‐alt‐BT)_0.5, shows the higher degree of crystallization, stronger π–π stacking, and broader absorption spectrum in the solid state, as compared to its alternating PDIDTDTBT analogue. Bulk heterojunction photovoltaic cells based on ITO/PEDOT:PSS/polymer:PC₇₁BM/Ca/Al configuration were fabricated and characterized. PDIDTDTBT /PC₇₁BM and PTDIDTTBT /PC₇₁BM systems exhibited promising power‐conversion efficiencies (PCEs) of 1.65 % and 2.00 %, respectively. Owing to the complementary absorption spectra, as well as the compatible structures of PDIDTDTBT and PTDIDTTBT , the PCE of the device based on the ternary blend PDIDTDTBT / PTDIDTTBT /PC₇₁BM was further improved to 2.40 %.     

Strongly Correlated Alignment of Fluorinated 5,11‐Bis(triethylgermylethynyl)anthradithiophene Crystallites in Solution‐Processed Field‐Effect Transistors

The crystallinity of an organic semiconductor film determines the efficiency of charge transport in electronic devices. This report presents a micro‐to‐nanoscale investigation on the crystal growth of fluorinated 5,11‐bis(triethylgermylethynyl)anthradithiophene (diF‐TEG‐ADT) and its implication for the electrical behavior of organic field‐effect transistors (OFETs). diF‐TEG‐ADT exhibits remarkable self‐assembly through spin‐cast preparation, with highly aligned edge‐on stacking creating a fast hole‐conducting channel for OFETs.     

Synthesis of a Novel Fused Thiophene‐thieno[3,2‐b]thiophene‐thiophene Donor Monomer and Co‐polymer for Use in OPV and OFETs

The synthesis of a novel fused hexacyclic electron rich monomer incorporating thieno[3,2‐b]thiophene is reported and characterized by single crystal X‐ray diffraction. Suzuki co‐polymerization with benzothiadiazole (BT) afforded a novel low band‐gap polymer P4TBT with high molecular weights and good solution processability. Bulk heterojunction solar cell devices using the P4TBT and [70]PCBM gave power conversion efficiencies of 2.5%. Top‐gate, bottom‐contact field effect transistors (FETs) using P4TBT displayed high hole mobilities of 0.07 cm² · Vs⁻¹ demonstrating the suitability of the novel monomer and polymer for use in high performing organic electronic devices.

     

Thienoacene‐Fused Pentalenes: Syntheses,Structures, Physical Properties and Applications for Organic Field‐Effect Transistors

Three soluble and stable thienoacene‐fused pentalene derivatives ( 1 – 3 ) with different π‐conjugation lengths were synthesized. X‐ray crystallographic analysis and density functional theory (DFT) calculations revealed their unique geometric and electronic structures due to the interaction between the aromatic thienoacene units and antiaromatic pentalene moiety. As a result, they all possess a small energy gap and show amphoteric redox behaviour. Time dependent (TD) DFT calculations were used to explain their unique electronic absorption spectra. These new compounds exhibited good thermal stability and ordered packing in solid state and thus their applications in organic field‐effect transistors (OFETs) were also investigated. The highest field‐effect hole mobility of 0.016, 0.036 and 0.001 cm² V^?1 s^?1 was achieved for solution‐processed thin films of 1 – 3 , respectively.     

Synthesis,characterization, and field‐effect transistor performance of poly[2,6‐bis(3‐tridecanoxythiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene]

A new copolymer of benzo[1,2‐b:4,5‐b′]dithiophene and 3,3′‐bis(tridecanoxy)‐5,5′‐bithiophene was synthesized through Stille copolymerization. The bis‐(3‐alkoxythiophene) monomer was synthesized through a silver fluoride mediated, palladium‐catalyzed cross‐coupling, in which bromide functional groups were preserved instead of consumed. The copolymer has been characterized and applied in field‐effect transistors, giving a hole mobility of 2 × 10^?3 cm²/Vs and an on/off ratio >10⁶, with negligible hysteresis, on standard silicon substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1973–1978, 2010     

A Solution‐Processable Molecule using Thieno[3,2‐b]thiophene as Building Block for Efficient Organic Solar Cells

A solution‐processed acceptor‐π‐donor‐π‐acceptor (A‐π‐D‐π‐A) type small molecule, namely DCATT, has been designed and synthesized for the application as donor material in organic solar cells. The fused aromatic unit thieno[3,2‐b]thiophene (TT) flanked with thiophene is applied as π bridge, while 4,8‐bisthienyl substituted benzodithiophene (BDT) and 2‐ethylhexyl cyanoacetate are chosen as the central building block and end group, respectively. Introduction of fused ring to the small molecule enhances the conjugation length of the main chain, and gives a strong tendency to form π–π stacking with a large overlapping area which favors to high charge carrier transport. Small‐molecule organic solar cells based on blends of DCATT and fullerene acceptor exhibit power conversion efficiencies as high as 5.20 % under the illumination of AM 1.5G, 100 mW cm^?2.     

Synthesis of a Novel Low‐Bandgap Polymer Based on a Ladder‐Type Heptacyclic Arene Consisting of Outer Thieno[3,2‐b]thiophene Units for Efficient Photovoltaic Application

A novel conjugated polymer PIDTT‐quinoxaline (Qx) based on the coplanar thieno[3,2‐b]thiophene‐phenylene‐thieno[3,2‐b]thiophene structure is synthesized and evaluated as an electron‐donor material for bulk‐heterojunction polymer solar cells (BHJ PSCs). The absorption spectra, electrochemical, charge transport, and film morphology properties as well as theoretical modeling of PIDTT‐Qx are investigated to understand its intrinsic structure–property relationship. As expected, this polymer with an extended π‐conjugated backbone exhibits a narrow‐bandgap and board absorption spectrum for enhanced light harvesting. BHJ PSCs (ITO/PEDOT:PSS/polymer:PC₇₁BM/interlayer/Al) afford a maximum power conversion efficiency of 5.05% with an open‐circuit voltage of 0.84 V, a short‐circuit current density of 11.26 mA cm⁻², and a fill factor of 53.4%. These results demonstrate the potential of PIDTT‐Qx as an efficient electron‐donor material for BHJ PSCs.

     

Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field‐Effect Transistors

A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition‐metal‐catalyzed C?H‐bond functionalization. In addition to modifying the substituents present on the end‐pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution‐state properties and field‐effect‐transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λ_max value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin‐film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm² V^?1 s^?1 and the I_on/I_off value is greater than 10⁶.     

Benzo[1,2‐b:4,5‐b′]dithiophene Building Block for the Synthesis of Semiconducting Polymers

This review covers the synthesis and polymerization of benzo[1,2‐b: 4,5‐b′]dithiophene (BDT) to generate semiconducting polymers used in organic field‐effect transistors (OFET) and organic solar cells applications.     

Electronic Properties and Photovoltaic Performances of a Series of Oligothiophene Copolymers Incorporating Both Thieno[3,2‐b]thiophene and 2,1,3‐Benzothiadiazole Moieties

A series of donor‐acceptor alternated conjugated copolymers, composed of thiophene, bithiophene, thieno[3,2‐b]thiophene, and 2,1,3‐benzothiadiazole units and differing from each other by the nature and the number of 3‐alkylthiophene in the backbone, have been synthesized by Stille cross‐coupling polymerization. The material's optical and electrochemical properties, in solution and in thin films, have been investigated using UV‐Visible absorption and cyclic voltammetry. Bulk heterojunction solar cells using blends of the newly synthesized copolymers, as electron donor, and C60‐PCBM or C70‐PCBM, as electron transporting material, have been elaborated. A maximum power conversion efficiency of 1.8% is achieved with a 1:4 PPBzT²‐C12:C70‐PCBM weight ratio.

     

Heteroanalogues of PCBM: N‐Bridged Imino‐PCBMs for Organic Field‐Effect Transistors

Crossing the bridge : Two isomeric iminofullerenes, [5,6]‐open azafulleroid 1 and [6,6]‐closed aziridinofullerene 2 , were prepared by cycloaddition of an organic azide to C₆₀. These “azalogues” enable the study of the effects of the bridging atom in a fullerene cage, that is, C₆₀‐like (5,6‐open) versus PCBM‐like (6,6‐closed), as a function of their π systems (PCBM=[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester).

     

Synthesis,Structures, and Properties of Fused Thiophenes for Organic Field‐Effect Transistors

A series of fused thiophenes composed of fused α‐oligothiophene units as building blocks, end‐capped with either styrene or 1‐pentyl‐4‐vinylbenzene groups, has been synthesized through Stille coupling reactions. The compounds have been fully characterized by means of ¹H NMR spectrometry, high‐resolution mass spectrometry, and elemental analysis. The molecules present a trans–trans configuration between their double bonds, which has been verified and confirmed by Fourier‐transform infrared spectroscopy and single‐crystal X‐ray diffraction analysis. The X‐ray crystal structures showed π–π overlap and sulfur–sulfur interactions between the adjacent molecules. The decomposition temperatures were all found to be above 300 °C, indicating that compounds of this series possess excellent thermal stability. The fact that no phase transition occurs at low temperature indicates that they should be well‐suited for application in devices. Moreover, they possess low HOMO energy levels, based on cyclic voltammetry measurements, and suitable energy gaps, as determined from their thin‐film UV/Vis spectra. Thin‐film X‐ray diffraction analysis and atomic force microscopy revealed high crystallinity on supporting substrates. In addition, as the substrate temperature has a significant influence on the morphology and the degree of crystallinity, the device performance could be optimized by varying the substrate temperature. These materials were found to exhibit optimal field‐effect performance, with a mobility of 0.17 cm² V^?1 s^?1 and an on/off ratio of 10⁵, at a substrate temperature of 70 °C.     

Design and synthesis of dithieno[3,2‐b:2′3′‐d]pyrrole‐based conjugated polymers for photovoltaic applications: consensus between low bandgap and low HOMO energy level

A strategy of the fine‐tuning of the degree of intrachain charge transfer and aromaticity of polymer backbone was adopted to design and synthesize new polymers applicable in photovoltaics. Three conjugated polymers P1 , P2 , and P3 were synthesized by alternating the electron‐donating dithieno[3,2‐b:2′3′‐d]pyrrole (D) and three different electron‐accepting (A) segments ( P1 : N‐(2‐ethylhexyl)phthalimide; P2 : 1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole; and P3 : thiophene‐3‐hexyl formate) in the polymer main chain. Among the three polymers, P2 possessed the broadest absorption band ranging from 300 to 760 nm, the lowest bandgap (1.63 eV), and enough low HOMO energy level (?5.27 eV) because of the strong intrachain charge transfer from D to A units and the appropriate extent of quinoid state in the main chain of P2 , which was convinced by the theoretical simulation of molecular geometry and front orbits. Photovoltaic study of solar cells based on the blends of P1 – P3 and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) demonstrated that P2 :PCBM exhibited the best performance: a power conversion efficiency of 1.22% with a high open‐circuit voltage (V_OC) of 0.70 V and a large short‐circuit current (I_SC) of 5.02 mA/cm² were achieved. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Solution‐Processable Balanced Ambipolar Field‐Effect Transistors Based on Carbonyl‐Regulated Copolymers

It is very important to develop ambipolar field effect transistors to construct complementary circuits. To obtain balanced hole‐ and electron‐transport properties, one of the key issues is to regulate the energy levels of the frontier orbitals of the semiconductor materials by structural tailoring, so that they match well with the electrode Fermi levels. Five conjugated copolymers were synthesized and exhibited low LUMO energy levels and narrow bandgaps on account of the strong electron‐withdrawing effect of the carbonyl groups. Polymer thin film transistors were prepared by using a solution method and exhibited high and balanced hole and electron mobility of up to 0.46 cm² V^?1 s^?1, which suggested that these copolymers are promising ambipolar semiconductor materials.     

Solution‐Grown Organic Single‐Crystalline Donor–Acceptor Heterojunctions for Photovoltaics

Organic single crystals are ideal candidates for high‐performance photovoltaics due to their high charge mobility and long exciton diffusion length; however, they have not been largely considered for photovoltaics due to the practical difficulty in making a heterojunction between donor and acceptor single crystals. Here, we demonstrate that extended single‐crystalline heterojunctions with a consistent donor‐top and acceptor‐bottom structure throughout the substrate can be simply obtained from a mixed solution of C₆₀ (acceptor) and 3,6‐bis(5‐(4‐n‐butylphenyl)thiophene‐2‐yl)‐2,5‐bis(2‐ethylhexyl)pyrrolo[3,4‐c]pyrrole‐1,4‐dione (donor). 46 photovoltaic devices were studied with the power conversion efficiency of (0.255±0.095) % under 1 sun, which is significantly higher than the previously reported value for a vapor‐grown organic single‐crystalline donor–acceptor heterojunction (0.007 %). As such, this work opens a practical avenue for the study of organic photovoltaics based on single crystals.     

Graphene Field‐Effect Transistors: Electrochemical Gating,Interfacial Capacitance,and Biosensing Applications

Single‐layer graphene has received much attention because of its unique two‐dimensional crystal structure and properties. In this review, we focus on the graphene devices in solution, and their properties that are relevant to chemical and biological applications. We will discuss their charge transport, controlled by electrochemical gates, interfacial and quantum capacitance, charged impurities, and surface potential distribution. The sensitive dependence of graphene charge transport on the surrounding environment points to their potential applications as ultrasensitive chemical sensors and biosensors. The interfacial and quantum capacitance studies are directly relevant to the on‐going effort of creating graphene‐based ultracapacitors for energy storage.