Imperial College London

ProfessorMartinHeeney

Faculty of Natural SciencesDepartment of Chemistry

Professor of Organic Materials
 
 
 
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Contact

 

+44 (0)20 7594 1248m.heeney Website

 
 
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Location

 

401GMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Publication Type
Year
to

300 results found

Taroni PJ, Santagiuliana G, Wan K, Calado P, Qiu M, Zhang H, Pugno NM, Palma M, Stingelin-Stutzman N, Heeney M, Fenwick O, Baxendale M, Bilotti Eet al., 2018, Toward Stretchable Self-Powered Sensors Based on the Thermoelectric Response of PEDOT:PSS/Polyurethane Blends, ADVANCED FUNCTIONAL MATERIALS, Vol: 28, ISSN: 1616-301X

Journal article

Wijeyasinghe N, Tsetseris L, Regoutz A, Sit WY, Fei Z, Du T, Wang X, Mclachlan MA, Vourlias G, Patsalas PA, Payne DJ, Heeney M, Anthopoulos TDet al., 2018, Copper (I) selenocyanate (CuSeCN) as a novel hole-transport layer for transistors, organic solar cells, and light-emitting diodes, Advanced Functional Materials, Vol: 28, ISSN: 1616-301X

The synthesis and characterization of copper (I) selenocyanate (CuSeCN) and its application as a solution-processable hole-transport layer (HTL) material in transistors, organic light-emitting diodes, and solar cells are reported. Density-functional theory calculations combined with X-ray photoelectron spectroscopy are used to elucidate the electronic band structure, density of states, and microstructure of CuSeCN. Solution-processed layers are found to be nanocrystalline and optically transparent ( > 94%), due to the large bandgap of ≥3.1 eV, with a valence band maximum located at -5.1 eV. Hole-transport analysis performed using field-effect measurements confirms the p-type character of CuSeCN yielding a hole mobility of 0.002 cm 2 V -1 s -1 . When CuSeCN is incorporated as the HTL material in organic light-emitting diodes and organic solar cells, the resulting devices exhibit comparable or improved performance to control devices based on commercially available poly(3,4-ethylenedioxythiophene):polystyrene sulfonate as the HTL. This is the first report on the semiconducting character of CuSeCN and it highlights the tremendous potential for further developments in the area of metal pseudohalides.

Journal article

Datko B, Fei Z, Heeney M, Grey Jet al., 2018, Effect of conformational changes on triplet formation in a heavy heteroatom conjugated polymer: Single polymer molecules and molecular aggregates, 255th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nexus of Food, Energy, and Water, Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727

Conference paper

Charlton RJ, Fogarty R, Bogatko S, Zuehlsdorff TJ, Hine NDM, Heeney MJ, Horsfield AP, Haynes PDet al., 2018, Implicit and explicit host effects on excitons in pentacene derivatives, Journal of Chemical Physics, Vol: 148, ISSN: 0021-9606

Anab initiostudy of the effects of implicit and explicit hosts on the excited state properties ofpentacene and its nitrogen-based derivatives has been performed using ground state density func-tional theory (DFT), time-dependent DFT and ∆SCF. We observe a significant solvatochromicredshift in the excitation energy of the lowest singlet state (S1) of pentacene from inclusion inap-terphenyl host compared to vacuum; for an explicit host consisting of six nearest neighbourp-terphenyls, we obtain a redshift of 65 meV while a conductor-like polarisable continuum model(CPCM) yields a 78 meV redshift. Comparison is made between the excitonic properties of pen-tacene and four of its nitrogen-based analogues, 1,8-, 2,9-, 5,12-, and 6,13-diazapentacene with thelatter found to be the most distinct due to local distortions in the ground state electronic struc-ture. We observe that a CPCM is insufficient to fully understand the impact of the host due tothe presence of a mild charge-transfer (CT) coupling between the chromophore and neighbouringp-terphenyls, a phenomenon which can only be captured using an explicit model. The strengthof this CT interaction increases as the nitrogens are brought closer to the central acene ring ofpentacene.

Journal article

Lu R, Han Y, Zhang W, Zhu X, Fei Z, Hodsden T, Anthopoulos TD, Heeney Met al., 2018, Alkylated indacenodithieno[3,2-b] thiophene-based all donor ladder-type conjugated polymers for organic thin film transistors, Journal of Materials Chemistry C, Vol: 6, Pages: 2004-2009, ISSN: 2050-7534

We report the synthesis of a series of indacenodithieno[3,2-b]thiophene (IDTT) based conjugated polymers by copolymerization with three different electron rich co-monomers [thiophene (T), thieno[3,2-b] thiophene (TT) and dithieno[3,2-b:2′,3′-d]thiophene (DTT)] under Stille coupling conditions. The resulting all-donor polymers show very good solubility in common solvents and exhibit similar optical, thermal and electronic properties. However, the performance of these semiconductors in thin film transistor devices varied and was highly dependent on the nature of the co-monomer. All polymers exhibited unipolar p-type charge transport behaviour, with the mobility values following the trend of IDTT-TT > IDTT-DTT > IDTT-T. The peak saturation mobility value of IDTT-TT was extracted to be 1.1 cm 2 V -1 s -1 , amongst the highest mobility for all-donor conjugated polymers reported to date.

Journal article

Fei Z, Eisner FD, Jiao X, Azzouzi M, Röhr JA, Han Y, Shahid M, Chesman ASR, Easton CD, McNeill CR, Anthopoulos TD, Nelson J, Heeney M, Heeney MJ, Fei Z, Jiao X, Eisner F, Azzouzi M, Rohr J, Han Y, Shahid M, Chesman A, Easton C, McNeill C, Nelson J, Anthopoulos Tet al., 2018, An alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor with high crystallinity exhibiting single junction solar cell efficiencies greater than 13% with low voltage losses, Advanced Materials, Vol: 30, ISSN: 0935-9648

A new synthetic route, to prepare an alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor (C8-ITIC), is reported. Compared to the reported ITIC with phenylalkyl side chains, the new acceptor C8-ITIC exhibits a reduction in the optical band gap, higher absorptivity, and an increased propensity to crystallize. Accordingly, blends with the donor polymer PBDB-T exhibit a power conversion efficiency (PCE) up to 12.4%. Further improvements in efficiency are found upon backbone fluorination of the donor polymer to afford the novel material PFBDB-T. The resulting blend with C8-ITIC shows an impressive PCE up to 13.2% as a result of the higher open-circuit voltage. Electroluminescence studies demonstrate that backbone fluorination reduces the energy loss of the blends, with PFBDB-T/C8-ITIC-based cells exhibiting a small energy loss of 0.6 eV combined with a high JSCof 19.6 mA cm-2.

Journal article

Datko BD, Thomas AK, Fei Z, Heeney M, Grey JKet al., 2017, Effect of a heavy heteroatom on triplet formation and interactions in single conjugated polymer molecules and aggregates, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, Vol: 19, Pages: 28239-28248, ISSN: 1463-9076

Journal article

Panidi J, Paterson AF, Khim D, Fei Z, Han Y, Tsetseris L, Vourlias G, Patsalas PA, Heeney M, Anthopoulos TDet al., 2017, Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C6F5)(3), Advanced Science, Vol: 5, ISSN: 2198-3844

Improving the charge carrier mobility of solution-processable organic semiconductors is critical for the development of advanced organic thin-film transistors and their application in the emerging sector of printed electronics. Here, a simple method is reported for enhancing the hole mobility in a wide range of organic semiconductors, including small-molecules, polymers, and small-molecule:polymer blends, with the latter systems exhibiting the highest mobility. The method is simple and relies on admixing of the molecular Lewis acid B(C6F5)3 in the semiconductor formulation prior to solution deposition. Two prototypical semiconductors where B(C6F5)3 is shown to have a remarkable impact are the blends of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene:poly(triarylamine) (diF-TESADT:PTAA) and 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene:poly(indacenodithiophene-co-benzothiadiazole) (C8-BTBT:C16-IDTBT), for which hole mobilities of 8 and 11 cm2 V−1 s−1, respectively, are obtained. Doping of the 6,13-bis(triisopropylsilylethynyl)pentacene:PTAA blend with B(C6F5)3 is also shown to increase the maximum hole mobility to 3.7 cm2 V−1 s−1. Analysis of the single and multicomponent materials reveals that B(C6F5)3 plays a dual role, first acting as an efficient p-dopant, and secondly as a microstructure modifier. Semiconductors that undergo simultaneous p-doping and dopant-induced long-range crystallization are found to consistently outperform transistors based on the pristine materials. Our work underscores Lewis acid doping as a generic strategy towards high performance printed organic microelectronics.

Journal article

Wade J, Wood S, Collado-Fregoso E, Heeney M, Durrant J, Kim J-Set al., 2017, Impact of Fullerene Intercalation on Structural and Thermal Properties of Organic Photovoltaic Blends, JOURNAL OF PHYSICAL CHEMISTRY C, Vol: 121, Pages: 20976-20985, ISSN: 1932-7447

The performance of organic photovoltaic blend devices is critically dependent on the polymer:fullerene interface. These interfaces are expected to impact the structural and thermal properties of the polymer with regards to the conjugated backbone planarity and transition temperatures during annealing/cooling processes. Here, we report the impact of fullerene intercalation on structural and thermal properties of poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT), a highly stable material known to exhibit liquid crystalline behavior. We undertake a detailed systematic study of the extent of intercalation in the PBTTT:fullerene blend, considering the use of four different fullerene derivatives and also varying the loading ratios. Resonant Raman spectroscopy allows direct observation of the interface morphology in situ during controlled heating and cooling. We find that small fullerene molecules readily intercalate into PBTTT crystallites, resulting in a planarization of the polymer backbone, but high fullerene loading ratios or larger fullerenes result in nonintercalated domains. During cooling from melt, nonintercalated blend films are found to return to their original morphology and reproduce all thermal transitions on cooling with minimal hysteresis. Intercalated blend films show significant hysteresis on cooling due to the crystallized fullerene attempting to reintercalate. The strongest hysteresis is for intercalated blend films with excess fullerene loading ratio, which form a distinct nanoribbon morphology and exhibit a reduced geminate recombination rate. These results reveal that careful consideration should be taken during device fabrication, as postdeposition thermal treatments significantly impact the charge generation and recombination dynamics.

Journal article

Wijeyasinghe N, Regoutz A, Eisner F, Du T, Tsetseris L, Lin Y-H, Faber H, Pattanasattayavong P, Li J, Yan F, McLachlan MA, Payne DJ, Heeney M, Anthopoulos TDet al., 2017, Copper(I) Thiocyanate (CuSCN) Hole-Transport Layers Processed from Aqueous Precursor Solutions and Their Application in Thin-Film Transistors and Highly Efficient Organic and Organometal Halide Perovskite Solar Cells, ADVANCED FUNCTIONAL MATERIALS, Vol: 27, ISSN: 1616-301X

This study reports the development of copper(I) thiocyanate (CuSCN) hole-transport layers (HTLs) processed from aqueous ammonia as a novel alternative to conventional n-alkyl sulfide solvents. Wide bandgap (3.4–3.9 eV) and ultrathin (3–5 nm) layers of CuSCN are formed when the aqueous CuSCN–ammine complex solution is spin-cast in air and annealed at 100 °C. X-ray photoelectron spectroscopy confirms the high compositional purity of the formed CuSCN layers, while the high-resolution valence band spectra agree with first-principles calculations. Study of the hole-transport properties using field-effect transistor measurements reveals that the aqueous-processed CuSCN layers exhibit a fivefold higher hole mobility than films processed from diethyl sulfide solutions with the maximum values approaching 0.1 cm2 V−1 s−1. A further interesting characteristic is the low surface roughness of the resulting CuSCN layers, which in the case of solar cells helps to planarize the indium tin oxide anode. Organic bulk heterojunction and planar organometal halide perovskite solar cells based on aqueous-processed CuSCN HTLs yield power conversion efficiency of 10.7% and 17.5%, respectively. Importantly, aqueous-processed CuSCN-based cells consistently outperform devices based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate HTLs. This is the first report on CuSCN films and devices processed via an aqueous-based synthetic route that is compatible with high-throughput manufacturing and paves the way for further developments.

Journal article

Green JP, Cryer SJ, Marafie J, White AJP, Heeney Met al., 2017, Synthesis of a Luminescent Arsolo[2,3-d:5,4-d']bis(thiazole) Building Block and Comparison to Its Phosphole Analogue, Organometallics, Vol: 36, Pages: 2632-2636, ISSN: 0276-7333

The synthesis of 4-phenyl-4H-arsolo[2,3-d:5,4-d′]bis(thiazole) is reported, and its properties are compared to those of the previously prepared phosphole analogue. By comparison of their single-crystal structures, the harmonic oscillator model of heterocyclic electron delocalization (HOMHED) was used to directly compare the aromatic character of the two systems. The findings demonstrate that, although both compounds can be considered aromatic, the phosphole-containing compound had a greater degree of aromatic character than its arsole analogue. The arsole derivative exhibited excellent stability in ambient air with no formation of the arsole oxide observed upon storage. The absorption and photoluminescence spectra of the arsole derivate were subtly altered in comparison to the phosphole derivative, suggesting that changing pnictogenic atoms in such fused-ring systems to heavier analogues could be a viable way of tuning both the ambient stability and optoelectronic properties of such materials.

Journal article

Fei Z, Chen L, Han Y, Gann E, Chesman ASR, McNeill CR, Anthopoulos TD, Heeney M, Pietrangelo Aet al., 2017, Alternating 5,5-Dimethylcyclopentadiene and Diketopyrrolopyrrole Copolymer Prepared at Room Temperature for High Performance Organic Thin-Film Transistors, Journal of the American Chemical Society, Vol: 139, Pages: 8094-8097, ISSN: 1520-5126

We report that the inclusion of nonaromatic 5,5-dimethylcyclopentadiene monomer into a conjugated backbone is an attractive strategy to high performance semiconducting polymers. The use of this monomer enables a room temperature Suzuki copolymerization with a diketopyrrolopyrrole comonomer to afford a highly soluble, high molecular weight material. The resulting low band gap polymer exhibits excellent photo and thermal stability, and despite a large π–π stacking distance of 4.26 Å, it demonstrates excellent performance in thin-film transistor devices.

Journal article

Fei Z, Han Y, Gann E, Hodsden T, Chesman ASR, McNeill CR, Anthopoulos TD, Heeney MJet al., 2017, Alkylated selenophene-based ladder-type monomers via a facileroute for high performance thin-film transistor applications, Journal of the American Chemical Society, Vol: 139, Pages: 8552-8561, ISSN: 1943-2984

We report the synthesis of two new selenophene-containing ladder-type monomers, cyclopentadiselenophene (CPDS) and indacenodiselenophene (IDSe), via a 2-fold and 4-fold Pd-catalyzed coupling with a 1,1-diborylmethane derivative. Copolymers with benzothiadiazole were prepared in high yield by Suzuki polymerization to afford materials which exhibited excellent solubility in a range of nonchlorinated solvents. The CPDS copolymer exhibited a band gap of just 1.18 eV, which is among the lowest reported for donor–acceptor polymers. Thin-film transistors were fabricated using environmentally benign, nonchlorinated solvents, with the CPDS and IDSe copolymers exhibiting hole mobility up to 0.15 and 6.4 cm2 V–1 s–1, respectively. This high performance was achieved without the undesirable peak in mobility often observed at low gate voltages due to parasitic contact resistance.

Journal article

Costa L, Al-Hashimi M, Heeney M, Terekhov A, Rajput D, Hofmeister W, Verma Aet al., 2017, Template-Synthesis of Conjugated Poly(3-Hexylselenophene) (P3HS) Nanofibers Using Femtosecond Laser Machined Fused Silica Templates, MRS ADVANCES, Vol: 2, Pages: 2957-2960, ISSN: 2059-8521

Journal article

Hu Z, Haws RT, Fei Z, Boufflet P, Heeney M, Rossky PJ, Vanden Bout DAet al., 2017, Impact of backbone fluorination on nanoscale morphology and excitonic coupling in polythiophenes, PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, Vol: 114, Pages: 5113-5118, ISSN: 0027-8424

Journal article

Creamer A, Casey A, Marsh AV, Shahid M, Gao M, Heeney Met al., 2017, Systematic Tuning of 2,1,3-Benzothiadiazole Acceptor Strength by Monofunctionalization with Alkylamine, Thioalkyl, or Alkoxy Groups in Carbazole Donor-Acceptor Polymers, MACROMOLECULES, Vol: 50, Pages: 2736-2746, ISSN: 0024-9297

A simple route to the preparation of alkylamine, thioalkyl, and alkoxy monofunctionalized 4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole) based monomers is reported from a common fluorinated precursor. Copolymerization with a carbazole comonomer under Suzuki conditions yielded a series of analogous donor–acceptor copolymers in which the only difference was the nature of the heteroatom (N, O, or S) on the benzothiadiazole core. This was shown to have a significant impact on the wavelength and intensity of the intramolecular charge transfer (ICT) absorption peak due to a combination of electronic and steric factors. Substantial differences were also observed in the solar cell performance of blends with PC71BM, with the octylamino substituted polymer exhibiting significantly lower performance than the other two polymers. This polymer also exhibited a reversible change in the optical spectra upon exposure to acid, suggesting potential as a sensing material.

Journal article

Casey A, Green JP, Shakya Tuladhar P, Kirkus M, Han Y, Anthopoulos TD, Heeney MJet al., 2017, Cyano substituted benzotriazole based polymers for use in organic solar cells, Journal of Materials Chemistry A, Vol: 5, Pages: 6465-6470, ISSN: 2050-7496

A new synthetic route to the electron accepting di-cyano substituted benzo[d][1,2,3]triazole (BTz) monomer 2-(2-butyloctyl)-4,7-di(thiophen-2-yl)-2H-benzotriazole-5,6-dicarbonitrile (dTdCNBTz) is reported. The cyano substituents can be easily introduced to the BTz unit in one step via the nucleophilic aromatic substitution of the fluorine substituents of the fluorinated precursor 2-(2-butyloctyl)-4,7-di(thiophen-2-yl)-2H-benzotriazole-5,6-difluoro (dTdFBTz). Co-polymers were prepared with distannylated benzo[1,2-b:4,5-b′]dithiophene (BDT) monomers containing either 2-ethylhexylthienyl (T-EH) side chains or 2-butyloctylthienyl (T-BO) side chains via Stille coupling to yield the novel medium band gap polymers P1 and P2 respectively. Whilst the organic photovoltaic (OPV) performance of P1 was limited by a lack of solubility, the improved solubility of P2 resulted in promising device efficiencies of up to 6.9% in blends with PC61BM, with high open circuit voltages of 0.95 V.

Journal article

Rodriquez D, Kim J-H, Root SE, Fe Z, Boufflet P, Heeney M, Kim T-S, Lipomi DJet al., 2017, Comparison of Methods for Determining the Mechanical Properties of Semiconducting Polymer Films for Stretchable Electronics, ACS APPLIED MATERIALS & INTERFACES, Vol: 9, Pages: 8855-8862, ISSN: 1944-8244

Journal article

Patra D, Lee J, Lee J, Sredojevic DN, White AJP, Bazzi HS, Brothers EN, Heeney M, Fang L, Yoon M-H, Al-Hashimi Met al., 2017, Synthesis of low band gap polymers based on pyrrolo[3,2-d:4,5-d ']bisthiazole (PBTz) and thienylenevinylene (TV) for organic thin-film transistors (OTFTs), JOURNAL OF MATERIALS CHEMISTRY C, Vol: 5, Pages: 2247-2258, ISSN: 2050-7526

Journal article

Isakov I, Paterson AF, Solomeshch O, Tessler N, Zhang Q, Li J, Zhang X, Fei Z, Heeney M, Anthopoulos TDet al., 2016, Hybrid complementary circuits based on p-channel organic and n-channel metal oxide transistors with balanced carrier mobilities of up to 10 cm(2)/Vs, Applied Physics Letters, Vol: 109, ISSN: 1077-3118

We report the development of hybrid complementary inverters based on p-channel organic andn-channel metal oxide thin-film transistors (TFTs) both processed from solution at <200 C. For theorganic TFTs, a ternary blend consisting of the small-molecule 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene, the polymer indacenodithiophene-benzothiadiazole (C16IDT-BT) and the p-typedopant C60F48 was employed, whereas the isotype In2O3/ZnO heterojunction was used for the nchannelTFTs. When integrated on the same substrate, p- and n-channel devices exhibited balancedcarrier mobilities up to 10 cm2/Vs. Hybrid complementary inverters based on these devices show highsignal gain (>30 V/V) and wide noise margins (70%). The moderate processing temperaturesemployed and the achieved level of device performance highlight the tremendous potential of the technologyfor application in the emerging sector of large-area microelectronics.

Journal article

Boufflet P, Casey A, Xia Y, Stavrinou PN, Heeney Met al., 2016, Pentafluorobenzene end-group as a versatile handle for para fluoro "click" functionalization of polythiophenes, Chemical Science, Vol: 8, Pages: 2215-2225, ISSN: 2041-6520

A convenient method of introducing pentafluorobenzene (PFB) as a single end-group in polythiophene derivatives is reported via in situ quenching of the polymerization. We demonstrate that the PFB-group is a particularly useful end-group due to its ability to undergo fast nucleophilic aromatic substitutions. Using this molecular handle, we are able to quantitatively tether a variety of common nucleophiles to the polythiophene backbone. The mild conditions required for the reaction allows sensitive functional moieties, such as biotin or a cross-linkable trimethoxysilane, to be introduced as end-groups. The high yield enabled the formation of a diblock rod-coil polymer from equimolar reactants under transition metal-free conditions at room temperature. We further demonstrate that water soluble polythiophenes end-capped with PFB can be prepared via the hydrolysis of an ester precursor, and that such polymers are amenable to functionalization under aqueous conditions.

Journal article

Casey A, Han Y, Gann E, Green JP, McNeill CR, Anthopoulos TD, Heeney Met al., 2016, Vinylene-linked oligothiophene–difluorobenzothiadiazole copolymer for transistor applications, ACS Applied Materials & Interfaces, Vol: 8, Pages: 31154-31165, ISSN: 1944-8244

The synthesis of the novel donor-acceptor monomer 4,7-bis[(E)-2-(5-bromo-3-dodecylylthiophen-2-yl)ethenyl]-5,6-difluoro-2,1,3-benzothiadiazole (FBT-V2T2) is reported. Polymerization with 4,4'-ditetradecyl-5,5'-bistrimethylstannyl-2,2'-bithiophene afforded a highly crystalline polymer that aggregated strongly in solution. Polymer films were well ordered resulting in high performance field-effect transistors with low onset voltages, negligible hysteresis, high channel current on/off ratios and peak hole mobilities of up to 0.5 cm2V-1s-1. Notably the transistors exhibited close to ideal behavior with extracted mobilities almost independent of gate of voltage.

Journal article

Boufflet P, Wood S, Wade J, Fei Z, Kim JS, Heeney Met al., 2016, Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties, Beilstein Journal of Organic Chemistry, Vol: 12, Pages: 2150-2163, ISSN: 1860-5397

The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV–visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems.

Journal article

Han Y, Barnes G, Lin Y-H, Martin J, Al-Hashimi M, AlQaradawi SY, Anthopoulos TD, Heeney Met al., 2016, Doping of large ionization potential indenopyrazine polymers via Lewis acid complexation with tris(pentafluorophenyl)borane: a simple method for improving the performance of organic thin-film transistors, Chemistry of Materials, Vol: 28, Pages: 8016-8024, ISSN: 1520-5002

Molecular doping, under certain circumstances, can be used to improve the charge transport in organic semiconductors through the introduction of excess charge carriers which can in turn negate unwanted trap states often present in organic semiconductors. Here, two Lewis basic indenopyrazine copolymers with large ionization potential (5.78 and 5.82 eV) are prepared to investigate the p-doping efficiency with the Lewis acid dopant, tris(pentafluorophenyl)borane, using organic thin-film transistors (OTFTs). The formation of Lewis acid–base complex between the polymer and dopant molecules is confirmed via optical spectroscopy and electrical field-effect measurements, with the latter revealing a dopant-concentration-dependent device performance. By adjusting the amount of p-dopant, the hole mobility can be increased up to 11-fold while the OTFTs’ threshold voltages are reduced. The work demonstrates an alternative doping mechanism other than the traditional charge transfer model, where the energy level matching principle can limit the option of dopants.

Journal article

Fei Z, Han Y, Martin J, Scholes FH, Al-Hashimi M, AlQaradawi SY, Stingelin N, Anthopoulos TD, Heeney Met al., 2016, Conjugated Copolymers of Vinylene Flanked Naphthalene Diimide, Macromolecules, Vol: 49, Pages: 6384-6393, ISSN: 0024-9297

We report the synthesis of a novel naphthalene diimide (NDI) monomer containing two (tributylstannyl)vinyl groups. The utility of this building block is demonstrated by its copolymerization with five different electron-rich comonomers under Stille conditions. The resulting high molecular weight polymers show red-shifted optical absorptions in comparison to the analogous polymers without the vinylene spacer and a significant increase in the intensity of the low-energy intramolecular charge transfer band. The polymers all exhibit ambipolar behavior in bottom-gate, top-contact organic thin-film transistors. The insertion of a solution-processed barium hydroxide layer between the polymer and the gold electrode led to unipolar behavior with improved electron mobilities.

Journal article

Paterson AF, Treat ND, Zhang W, Fei Z, Wyatt-Moon G, Faber H, Vourlias G, Patsalas PA, Solomeshch O, Tessler N, Heeney M, Anthopoulos TDet al., 2016, Small Molecule/Polymer Blend Organic Transistors with Hole Mobility Exceeding 13 cm V−1 s−1, Advanced Materials, Vol: 28, Pages: 7791-7798, ISSN: 1521-4095

A ternary organic semiconducting blend composed of a small-molecule, a conjugated polymer, and a molecular p-dopant is developed and used in solution-processed organic transistors with hole mobility exceeding 13 cm(2) V(-1) s(-1) (see the Figure). It is shown that key to this development is the incorporation of the p-dopant and the formation of a vertically phase-separated film microstructure.

Journal article

Casey A, Dimitrov SD, Shakya-Tuladhar P, Fei Z, Nguyen M, Han Y, Anthopoulos TD, Durrant JR, Heeney Met al., 2016, Effect of Systematically Tuning Conjugated Donor Polymer Lowest Unoccupied Molecular Orbital Levels via Cyano Substitution on Organic Photovoltaic Device Performance, Chemistry of Materials, Vol: 28, Pages: 5110-5120, ISSN: 0897-4756

We report a systematic study into the effects of cyano substitution on the electron accepting ability of the common acceptor 4,7-bis(thiophen-2-yl)-2,1,3-benzothiadiazole (DTBT). We describe the synthesis of DTBT monomers with either 0, 1, or 2 cyano groups on the BT unit and their corresponding copolymers with the electron rich donor dithienogermole (DTG). The presence of the cyano group is found to have a strong influence on the optoelectronic properties of the resulting donor–acceptor polymers, with the optical band gap red-shifting by approximately 0.15 eV per cyano substituent. We find that the polymer electron affinity is significantly increased by ∼0.25 eV upon addition of each cyano group, while the ionization potential is less strongly affected, increasing by less than 0.1 eV per cyano substituent. In organic photovoltaic (OPV) devices power conversion efficiencies (PCE) are almost doubled from around 3.5% for the unsubstituted BT polymer to over 6.5% for the monocyano substituted BT polymer. However, the PCE drops to less than 1% for the dicyano substituted BT polymer. These differences are mainly related to differences in the photocurrent, which varies by 1 order of magnitude between the best (1CN) and worst devices (2CN). The origin of this variation in the photocurrent was investigated by studying the charge generation properties of the photoactive polymer–fullerene blends using fluorescence and transient absorption spectroscopic techniques. These measurements revealed that the improved photocurrent of 1CN in comparison to 0CN was due to improved light harvesting properties while maintaining a high exciton dissociation yield. The addition of one cyano group to the BT unit optimized the position of the polymer LUMO level closer to that of the electron acceptor PC71BM, such that the polymer’s light harvesting properties were improved without sacrificing either the exciton dissociation yield or device VOC. We also identify that the dr

Journal article

Kang K, Watanabe S, Broch K, Sepe A, Brown A, Nasrallah I, Nikolka M, Fei Z, Heeney M, Matsumoto D, Marumoto K, Tanaka H, Kuroda SI, Sirringhaus Het al., 2016, 2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion, Nature Materials, Vol: 15, Pages: 896-902, ISSN: 1476-4660

Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

Journal article

Green J, Han Y, Kilmurray R, McLachlan M, Anthopoulos T, Heeney MJet al., 2016, An Air-Stable Semiconducting Polymer Containing Dithieno[3,2-b:2′,3′-d]arsole, Angewandte Chemie - International Edition, Vol: 55, Pages: 7148-7151, ISSN: 1433-7851

Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2-b;2′,3′-d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements.

Journal article

Green JP, Han Y, Kilmurray R, McLachlan MA, Anthopoulos TD, Heeney Met al., 2016, An air-stable semiconducting polymer containing Dithieno[3,2- b :2′,3′- d ]arsole, Angewandte Chemie, Vol: 128, Pages: 7264-7267, ISSN: 0044-8249

Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2-b;2′,3′-d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements.

Journal article

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