Poly(2,5-bis(2-octyldodecyl)-3,6-di(furan-2-yl)-2,5-dihydro-pyrrolo[3,4-c] pyrrole-1,4-dione-co-thieno[3,2-b]thiophene): A high performance polymer semiconductor for both organic thin film transistors and organic photovoltaics

A new diketopyrrolopyrrole (DPP)-containing donor-acceptor polymer, poly(2,5-bis(2-octyldodecyl)-3,6-di(furan-2-yl)-2,5-dihydro-pyrrolo[3,4-c] pyrrole-1,4-dione-co-thieno[3,2-b]thiophene) (PDBF-co-TT), is synthesized and studied as a semiconductor in organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). High hole mobility of up to 0.53 cm 2 V -1 s -1 in bottom-gate, top-contact OTFT devices is achieved owing to the ordered polymer chain packing and favoured chain orientation, strong intermolecular interactions, as well as uniform film morphology of PDBF-co-TT. The optimum band gap of 1.39 eV and high hole mobility make this polymer a promising donor semiconductor for the solar cell application. When paired with a fullerene acceptor, PC 71BM, the resulting OPV devices show a high power conversion efficiency of up to 4.38% under simulated standard AM1.5 solar illumination.

3,6-Di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione and bithiophene copolymer with rather disordered chain orientation showing high mobility in organic thin film transistors

Pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione or diketopyrrolopyrrole (DPP) is a useful electron-withdrawing fused aromatic moiety for the preparation of donor-acceptor polymers as active semiconductors for organic electronics. This study uses a DPP-furan-containing building block, 3,6-di(furan-2-yl)pyrrolo[3,4- c]pyrrole-1,4(2H,5H)-dione (DBF), to couple with a 2,2′-bithiophene unit, forming a new donor-acceptor copolymer, PDBFBT. Compared to its structural analogue, 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBT), DBF is found to cause blue shifts of the absorption spectra both in solution and in thin films and a slight reduction of the highest occupied molecular orbital (HOMO) energy level of the resulting PDBFBT. Despite the fact that its thin films are less crystalline and have a rather disordered chain orientation in the crystalline domains, PDBFBT shows very high hole mobility up to 1.54 cm 2 V-1 s-1 in bottom-gate, top-contact organic thin film transistors.

Solution processable poly(2,5-dialkyl-2,5-dihydro-3,6-di-2-thienyl- pyrrolo[3,4-c]pyrrole-1,4-dione) for ambipolar organic thin film transistors

Solution processable diketopyrrolopyrrole (DPP)-bithiophene polymers (PDBT) with long branched alkyl side chains on the DPP unit are synthesized. These polymers have favourable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for the injection and transport of both holes and electrons. Organic thin film transistors (OTFTs) using these polymers as semiconductors and gold as source/drain electrodes show typical ambipolar characteristics with very well balanced high hole and electron mobilities (μ h = 0.024 cm 2 V -1 s -1 and μ e = 0.056 cm 2 V -1 s -1). These simple and high-performing polymers are promising materials for ambipolar organic thin film transistors for low-cost CMOS-like logic circuits.

Design and modification of three-component randomly incorporated copolymers for high performance organic photovoltaic applications

In this study we report the molecular design, synthesis, characterization, and photovoltaic properties of a series of diketopyrrolopyrrole (DPP) and dithienothiophene (DTT) based donor-acceptor random copolymers. The six random copolymers are obtained via Stille coupling polymerization using various concentration ratios of donor to acceptor in the conjugated backbone. Bis(trimethylstannyl)thiophene was used as the bridge block to link randomly with the two comonomers 5-(bromothien-2-yl)-2,5-dialkylpyrrolo[3,4-c]pyrrole-1, 4-dione and 2,6-dibromo-3,5-dipentadecyl-dithieno[3,2-b;2′,3′-d] thiophene. The optical properties of these copolymers clearly reveal a change in the absorption band through optimization of the donor-acceptor ratio in the backbone. Additionally, the solution processability of the copolymers is modified through the attachment of different bulky alkyl chains to the lactam N-atoms of the DPP moiety. Applications of the polymers as light-harvesting and electron-donating materials in solar cells, in conjunction with PCBM as acceptor, show power conversion efficiencies (PCEs) of up to 5.02%.

Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Synthesis of diketopyrrolopyrrole based copolymers via the direct arylation method for p-channel and ambipolar OFETs

In this paper, we have synthesized two novel diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) copolymers poly{3,6-dithiophene-2-yl-2,5-di(2-octyl)- pyrrolo[3,4-c]pyrrole-1,4-dione-alt-1,5-bis(dodecyloxy)naphthalene} (PDPPT-NAP) and poly{3,6-dithiophene-2-yl-2,5-di(2-butyldecyl)-pyrrolo[3,4-c]pyrrole-1,4- dione-alt-2-dodecyl-2H-benzo[d][1,2,3]triazole} (PDPPT-BTRZ) via direct arylation organometallic coupling. Both copolymers contain a common electron withdrawing DPP building block which is combined with electron donating alkoxy naphthalene and electron withdrawing alkyl-triazole comonomers. The number average molecular weight (Mn) determined by gel permeation chromatography (GPC) for polymer PDPPT-NAP is around 23 400 g mol-1 whereas for polymer PDPPT-BTRZ it is 18 600 g mol-1. The solid state absorption spectra of these copolymers show a wide range of absorption from 400 nm to 1000 nm with optical band gaps calculated from absorption cut off values in the range of 1.45-1.30 eV. The HOMO values determined for PDPPT-NAP and PDPPT-BTRZ copolymers from photoelectron spectroscopy in air (PESA) data are 5.15 eV and 5.25 eV respectively. These polymers exhibit promising p-channel and ambipolar behaviour when used as an active layer in organic thin-film transistor (OTFT) devices. The highest hole mobility measured for polymer PDPPT-NAP is around 0.0046 cm2 V-1 s-1 whereas the best ambipolar performance was calculated for PDPPT-BTRZ with a hole and electron mobility of 0.01 cm2 V-1 s-1 and 0.006 cm2 V-1 s-1.

A furan-containing conjugated polymer for high mobility ambipolar organic thin film transistors

Furan substituted diketopyrrolopyrrole (DBF) combined with benzothiadiazole based polymer semiconductor PDPP-FBF has been synthesized and evaluated as an ambipolar semiconductor in organic thin-film transistors. Hole and electron mobilities as high as 0.20 cm 2 V -1 s -1 and 0.56 cm 2 V -1 s -1, respectively, are achieved for PDPP-FBF.

A fluorenone based low band gap solution processable copolymer for air stable and high mobility organic field effect transistors

A fluorenone based alternating copolymer (PFN-DPPF) with a furan based fused aromatic moiety has been designed and synthesized. PFN-DPPF exhibits a small band gap with a lower HOMO value. Testing this polymer semiconductor as the active layer in organic thin-film transistors results in hole mobilities as high as 0.15 cm2 V-1 s-1 in air.

Furan containing diketopyrrolopyrrole copolymers : synthesis, characterization, organic field effect transistor performance and photovoltaic properties

In this work, we report design, synthesis and characterization of solution processable low band gap polymer semiconductors, poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-phenylene} (PDPP-FPF), poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene} (PDPP-FNF) and poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-anthracene} (PDPP-FAF) using the furan-containing 3,6-di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBF) building block. As DBF acts as an acceptor moiety, a series of donor-acceptor (D-A) copolymers can be generated when it is attached alternatively with phenylene, naphthalene or anthracene donor comonomer blocks. Optical and electrochemical characterization of thin films of these polymers reveals band gaps in the range of 1.55-1.64 eV. These polymers exhibit excellent hole mobility when used as the active layer in organic thin-film transistor (OTFT) devices. Among the series, the highest hole mobility of 0.11 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices using PDPP-FNF. When these polymers are used as a donor and [70]PCBM as the acceptor in organic photovoltaic (OPV) devices, power conversion efficiencies (PCE) of 2.5 and 2.6% are obtained for PDPP-FAF and PDPP-FNF polymers, respectively. Such mobility values in OTFTs and performance in OPV make furan-containing DBF a very promising block for designing new polymer semiconductors for a wide range of organic electronic applications.

A benzothiadiazole end capped donor–acceptor based small molecule for organic electronics

A benzothiadiazole end-capped small molecule 3,6-bis(5-(benzo[c][1,2,5] thiadiazol-4-yl)thiophen-2-yl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-1, 4(2H,5H)-dione (BO-DPP-BTZ) using a fused aromatic moiety DPP (at the centre) is designed and synthesized. BO-DPP-BTZ is a donor-acceptor-donor (D-A-D) structure which possesses a band gap of 1.6 eV and exhibits a strong solid state ordering inferred from ∼120 nm red shift of the absorption maxima from solution to thin film. Field-effect transistors utilizing a spin coated thin film of BO-DPP-BTZ as an active layer exhibited a hole mobility of 0.06 cm 2 V-1 s-1. Solution-processed bulk heterojunction organic photovoltaics employing a blend of BO-DPP-BTZ and [70]PCBM demonstrated a power conversion efficiency of 0.9%.

Furan substituted diketopyrrolopyrrole and thienylenevinylene based low band gap copolymer for high mobility organic thin film transistors

A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4- c]pyrrole-1,4-dione-alt-thienylenevinylene} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (Eoptg) calculated from the polymer film absorption onset is around 1.37 eV. The π-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 °C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10 6-10 7. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

Water-based nanoparticulate solar cells using a diketopyrrolopyrrole donor polymer

Organic photovoltaic devices with either bulk heterojunction (BHJ) or nanoparticulate (NP) active layers have been prepared from a 1:2 blend of (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) (PDPP-TNT) and the fullerene acceptor, ([6,6]-phenyl C71-butyric acid methyl ester) (PC70BM). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been used to investigate the morphology of the active layers of the two approaches. Mild thermal treatment of the NP film is required to promote initial joining of the NPs in order for the devices to function, however the NP structure is retained. Consequently, whereas gross phase segregation of the active layer occurs in the BHJ device spin cast from chloroform, the nanoparticulate approach retains control of the material domain sizes on the length scale of exciton diffusion in the materials. As a result, NP devices are found to generate more than twice the current density of BHJ devices and have a substantially greater overall efficiency. The use of aqueous nanoparticulate dispersions offers a promising approach to control the donor acceptor morphology on the nanoscale with the benefit of environmentally- friendly, solution-based fabrication. © 2014 the Owner Societies.

Nanoscale phase domain structure and associated device performance of organic solar cells based on a diketopyrrolopyrrole polymer

We investigate the blend morphology and performance of bulk heterojunction organic photovoltaic devices comprising the donor polymer, pDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) and the fullerene acceptor, [70]PCBM ([6,6]-phenyl C71-butyric acid methyl ester). The blend morphology is heavily dependent upon the solvent system used in the fabrication of thin films. Thin films spin-coated from chloroform possess a cobblestone-like morphology, consisting of thick, round-shaped [70]PCBM-rich mounds separated by thin polymer-rich valleys. The size of the [70]PCBM domains is found to depend on the overall film thickness. Thin films spin-coated from a chloroform:dichlorobenzene mixed solvent system are smooth and consist of a network of pDPP-TNT nanofibers embedded in a [70]PCBM-rich matrix. Rinsing the films in hexane selectively removes [70]PCBM and allows for analysis of domain size and purity. It also provides a means for investigating exciton dissociation efficiency through relative photoluminescence yield measurements. Devices fabricated from chloroform solutions show much poorer performance than the devices fabricated from the mixed solvent system; this disparity in performance is seen to be more pronounced with increasing film thickness. The primary cause for the improved performance of devices fabricated from mixed solvents is attributed to the greater donor-acceptor interfacial area and resulting greater capacity for charge carrier generation.

A non-fullerene electron acceptor based on fluorene and diketopyrrolopyrrole building blocks for solution-processable organic solar cells with an impressive open-circuit voltage

A novel solution-processable non-fullerene electron acceptor 6,6′-(5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP1) based on fluorene and diketopyrrolopyrrole conjugated moieties was designed, synthesized and fully characterized. DPP1 exhibited excellent solubility and high thermal stability which are essential for easy processing. Upon using DPP1 as an acceptor with the classical electron donor poly(3-hexylthiophene), solution processable bulk-heterojunction solar cells afforded a power conversion efficiency of 1.2% with a high open-circuit voltage (1.1 V). As per our knowledge, this value of open circuit voltage is one of the highest values reported so far for a bulk-heterojunction device using DPP1 as a non-fullerene acceptor.

Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.