Cyano-substituted Polymer Research Articles

On-surface synthesis of two types of cyano-substituted polyfluorene derivatives via Ullmann coupling on Au(111).

Using 4-(3,6-dibromo-9H-carbazol-9-yl)benzonitrile (DBCB) precursors, we successfully constructed two types of cyano-substituted polymers on Au(111) by the molecular beam epitaxy method. According to the geometry, the two polymers are referred to as w-type polymers composed of cis-dimers and z-type polymers composed of trans-dimers. The intermediate dimers and final polymers were well characterized by high-resolution scanning tunneling microscopy (HR-STM). Moreover, the productivities of these two polymers can be controlled by adjusting the heating rate and different treatment methods. High heating rates and hot deposition can provide more ample space and time for molecular diffusion, which is conducive to the formation of w-type polymers with relatively low density. In addition, by combining scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations, we have shown that the addition of CN groups reduces the band gap of the two polymers. Our investigation thus shows the controllable construction of nanostructures through efficient surface synthesis parameters and reveals the potential of using functional groups as tools to modify the electronic properties of polymers.

A theoretical exploration of the effect of fluorine and cyano substitutions in diketopyrrolopyrrole-based polymer donor for organic solar cells

A series of polymer donor materials 1-5 based on diketopyrrolopyrrole and thiophene unit which have been widely used in organic solar cells (OSCs) were investigated based on quantum chemical calculations. The effect of fluorine and cyano substitutions in polymer donor materials was focused on. Based on the investigation on electronic structures and optical properties of the reported molecules 1 and 2 and the analysis on some parameters relevant to charge dissociation ability at donor/acceptor interface constituted by 1 and 2 with PC61BM such as intermolecular charge transfer and recombination, driving force and Coulombic bound energy, we explained why fluorine substitution can improve OPV efficiency through strengthening eletron-withdrawing ability from a theoretical perspective. Then we designed cyano-substituted polymers 3-5 with the aim of obtaining better photovoltaic donor materials. The results reveal that our attempt to design donor materials which can balance large open-circuit voltage (Voc) and high short-circuit current (Jsc) in OSCs has worked out. It is worth noting that the substitutions of fluorine and cyano groups synergistically reduce energy gap and HOMO energy level of polymers 3 and 4. Moreover, 3/PC61BM and 4/PC61BM heterojunctions show over 107 and 104 times higher than 1/PC61BM on the ratios of intermolecular charge transfer and recombination rates (kinter-CT/kinter-CR). Thus, our work here may provide an efficient strategy to design promising donor materials in OPVs and we hope it could be useful in the future experimental synthesis.

Effects of cyano-substituents on the molecular packing structures of conjugated polymers for bulk-heterojunction solar cells.

The molecular packing structures of two conjugated polymers based on alkoxy naphthalene, one with cyano-substituents and one without, have been investigated to determine the effects of electron-withdrawing cyano-groups on the performance of bulk-heterojunction solar cells. The substituted cyano-groups facilitate the self-assembly of the polymer chains, and the cyano-substituted polymer:PC71BM blend exhibits enhanced exciton dissociation to PC71BM. Moreover, the electron-withdrawing cyano-groups lower the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of the conjugated polymer, which leads to a higher open circuit voltage (V(OC)) and a lower energy loss during electron transfer from the donor to the acceptor. A bulk-heterojunction device fabricated with the cyano-substituted polymer:PC71BM blend has a higher V(OC) (0.89 V), a higher fill factor (FF) (51.4%), and a lower short circuit current (J(SC)) (7.4 mA/cm(2)) than that of the noncyano-substituted polymer:PC71BM blend under AM 1.5G illumination with an intensity of 100 mW cm(-2). Thus, the cyano-substitution of conjugated polymers may be an effective strategy for optimizing the domain size and crystallinity of the polymer:PC71BM blend, and for increasing V(OC) by tuning the HOMO and LUMO energy levels of the conjugated polymer.

Development of Polymer Acceptors for Organic Photovoltaic Cells

This review provides a current status report of the various n-type polymer acceptors for use as active materials in organic photovoltaic cells (OPVs). The polymer acceptors are divided into four categories. The first section of this review focuses on rylene diimide-based polymers, including perylene diimide, naphthalene diimide, and dithienocoronene diimide-based polymers. The high electron mobility and good stability of rylene diimides make them suitable for use as polymer acceptors in OPVs. The second section deals with fluorene and benzothiadiazole-based polymers such as poly(9,9’-dioctylfluorene-co-benzothiadiazole), and the ensuing section focuses on the cyano-substituted polymer acceptors. Cyano-poly(phenylenevinylene) and poly(3-cyano-4-hexylthiophene) have been used as acceptors in OPVs and exhibit high electron affinity arising from the electron-withdrawing cyano groups in the vinylene group of poly(phenylenevinylene) or the thiophene ring of polythiophene. Lastly, a number of other electron-deficient groups such as thiazole, diketopyrrolopyrrole, and oxadiazole have also been introduced onto polymer backbones to induce n-type characteristics in the polymer. Since the first report on all-polymer solar cells in 1995, the best power conversion efficiency obtained with these devices to date has been 3.45%. The overall trend in the development of n-type polymer acceptors is presented in this review.

Triplet formation from the charge-separated state in blends of MDMO-PPV with cyano-containing acceptor polymers

Polymer blends of MDMO-PPV with three different electron accepting cyano-substituted polymers have been investigated with photoinduced absorption (PIA) spectroscopy. In these blends, an efficient photoinduced charge transfer occurs that quenches the photoluminescence and produces a significant photovoltaic effect when the blends are incorporated as active layer into a solar cell configuration. Surprisingly, PIA spectroscopy in the millisecond time domain reveals that in the blends neutral triplet photoexcitations are almost exclusively formed in favor of polaronic charge carriers with yields higher than in the individual polymers. In the blends, the triplet state resides on the component with the lowest optical bandgap. The enhanced triplet generation is rationalized by the recombination of photogenerated charge carriers into a triplet state. This process may occur when the energy of the charge-separated state is higher than that of the triplet state. We demonstrate that this process is likely to occur in polymer solar cells with a high open-circuit voltage.

Charge- and energy-transfer processes at polymer/polymer interfaces: A joint experimental and theoretical study

When an exciton approaches the interface between two conjugated polymers, either energy or charge transfer can take place. We present a detailed experimental investigation of these processes in various binary polymer systems. The results are interpreted in the context of quantum-chemical calculations that provide estimates of the relative energies of intrachain versus interchain excited states in pairs of various PPV-related chains. In particular, we show that charge-transfer occurs at the interface between MEH-PPV and a cyanosubstituted PPV derivative, whereas energy transfer takes place at the interface of PPV with the same cyanosubstituted polymer. @S0163-1829~99!08031-5#

Excited-state energy- and charge-transfer at polymer/polymer interfaces

Abstract When an exciton diffuses to the interface between two conjugated polymers, either energy- or charge-transfermay take place. We present an experimental investigation of these processes in various binary polymer systems. These results are consistent with calculations of the relative energies of the intrachain and interchain excited states on pairs of different PPV-related chains. In particular, we show experimentally and theoretically that charge transfer occurs at the interface between MEH-PPV and a cyano-substituted PPV derivative, whereas energy transfer occurs at the interface of PPV with the same cyano-substituted polymer.

Trends in geometric and electronic properties of thiophene‐ and cyclopentadiene‐based polymers

In this work, we present theoretical evidence illustrating that cyano derivatives of conducting polymers such as polythiophene, polycyclopentadiene, and polyfulvene have smaller intrinsic band gaps than those of their parent polymers. The geometric and electronic properties of the parent and the derivative polymers were studied with the use of two methodologies: (1) the pseudo-one-dimensional band-structure calculations performed using the semi-empirical molecular orbital theory (MNDO, AM1) and (2) oligomer calculations performed using the ab initio molecular orbital theory both at the Hartree–Fock and configuration interaction levels. In particular, we found that an organic polymer, poly(dicyanomethylene cyclopentadifulvene) (PCNFv), has a comparable (possibly lower) band gap to the one observed in poly(dicyanomethylene cyclopentadithiophene) (PCNTH) (which has a band gap of 0.8 eV). The precursor of PCNFv is poly(dicyanomethylene cyclopentadicyclopentadiene) (PCNCY) in which two cyclopentadiene rings are connected by a dicyanomethylene group. The additional bond conjugation (in contrast to PCNCY) perpendicular to the chain axis makes PCNFv very rigid and fully planar. Trends in structural properties indicate that the lower band gaps in the cyano-substituted polymers, in comparison to their parent polymers, are accompanied by a decrease in bond alternations in the aromatic or trans–cisoid forms and by an increase in bond alternations in the quinoid or cis–transoid forms. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66: 229–240, 1998

Trends in geometric and electronic properties of thiophene- and cyclopentadiene-based polymers

In this work, we present theoretical evidence illustrating that cyano derivatives of conducting polymers such as polythiophene, polycyclopentadiene, and polyfulvene have smaller intrinsic band gaps than those of their parent polymers. The geometric and electronic properties of the parent and the derivative polymers were studied with the use of two methodologies: (1) the pseudo-one-dimensional band-structure calculations performed using the semi-empirical molecular orbital theory (MNDO, AM1) and (2) oligomer calculations performed using the ab initio molecular orbital theory both at the Hartree–Fock and configuration interaction levels. In particular, we found that an organic polymer, poly(dicyanomethylene cyclopentadifulvene) (PCNFv), has a comparable (possibly lower) band gap to the one observed in poly(dicyanomethylene cyclopentadithiophene) (PCNTH) (which has a band gap of 0.8 eV). The precursor of PCNFv is poly(dicyanomethylene cyclopentadicyclopentadiene) (PCNCY) in which two cyclopentadiene rings are connected by a dicyanomethylene group. The additional bond conjugation (in contrast to PCNCY) perpendicular to the chain axis makes PCNFv very rigid and fully planar. Trends in structural properties indicate that the lower band gaps in the cyano-substituted polymers, in comparison to their parent polymers, are accompanied by a decrease in bond alternations in the aromatic or trans–cisoid forms and by an increase in bond alternations in the quinoid or cis–transoid forms. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66: 229–240, 1998

Synthesis and characterization of polymer precursors bearing 2,2-dicyanovinyl groups and their curing to thermally stable and electrically conductive resins

4-Carboxybenzaldehyde was condensed with malononitrile to afford 1-(2,2-dicyanovinyl)-4-benzoic acid, which was converted to the corresponding acid chloride. The latter reacted with half the molar amount of an aromatic diamine or bisphenol to yield cyano-substituted polymer precursors. Crosslinked polymers were obtained by curing at 300°C for 40–60 h, which were stable up to 333–400°C in N 2 or air and afforded anaerobic char yield of 35–60% at 800°C. Prior to pyrolysis all polymer precursors are of amorphous structure and behave, at room temperature, as insulators. A dramatic decrease of the electrical resistivity is observed with increasing pyrolysis temperature. All resulting conductive materials exhibited crystalline structure revealed by their X-ray diffraction profiles. The temperature dependence of the electrical resistivity in the range −173 to 327°C (100 to 600 K) of all pyrolysed materials suggests that they have semiconducting properties. The variable-range hopping model as well as a thermally activated conduction model were applied in order to interpret the experimental data. The observed electrical conductivity seems to be thermally activated and may be associated with intermolecular and intramolecular hopping conduction processes. The activation energies for the intermolecular process range from 0.265 to 0.012 eV and for the intramolecular process from 0.380 to 0.047 eV, depending on the pyrolysis temperature. The electrical behaviour of all conductive materials can be easily controlled, from insulating to semiconducting, by controlling both the pyrolysis temperature and duration. The highest electrical conductivity of 20 S cm −1 has been obtained for two samples pyrolysed at 800°C for 40 h.