Sungu Hwang

Semi-crystalline photovoltaic polymers with efficiency exceeding 9% in a ∼300 nm thick conventional single-cell device

We report a series of semi-crystalline, low band gap (LBG) polymers and demonstrate the fabrication of highly efficient polymer solar cells (PSCs) in a thick single-cell architecture. The devices achieve a power conversion efficiency (PCE) of over 7% without any post-treatment (annealing, solvent additive, etc.) and outstanding long-term thermal stability for 200 h at 130 °C. These excellent characteristics are closely related to the molecular structures where intra- and/or intermolecular noncovalent hydrogen bonds and dipole–dipole interactions assure strong interchain interactions without losing solution processability. The semi-crystalline polymers form a well-distributed nano-fibrillar networked morphology with PC70BM with balanced hole and electron mobilities (a h/e mobility ratio of 1–2) and tight interchain packing (a π–π stacking distance of 3.57–3.59 A) in the blend films. Furthermore, the device optimization with a processing additive and methanol treatment improves efficiencies up to 9.39% in a ∼300 nm thick conventional single-cell device structure. The thick active layer in the PPDT2FBT:PC70BM device attenuates incident light almost completely without damage in the fill factor (0.71–0.73), showing a high short-circuit current density of 15.7–16.3 mA cm−2. Notably, PPDT2FBT showed negligible changes in the carrier mobility even at ∼1 μm film thickness.

Efficient conventional- and inverted-type photovoltaic cells using a planar alternating polythiophene copolymer.

A low-band-gap alternating copolymer, poly{5,6-bis(octyloxy)-4-(thiophen-2-yl)benzo[c]-1,2,5-thiadiazole} (PTBT), was synthesized and investigated for photovoltaic applications. PTBT showed a minimized torsion angle in its main backbone owing to the introduction of solubilizing octyloxy groups on the electron-poor benzothiadiazole unit, thereby resulting in pronounced intermolecular ordering and a deep level of the HOMO (-5.41 eV). By blending PTBT with [6,6]phenyl-C61-butyric acid methyl ester (PC(61)BM), highly promising performance was achieved with power-conversion efficiencies (PCEs) of 5.9 and 5.3% for the conventional and inverted devices, respectively, under air mass 1.5 global (AM 1.5G, 100 mW cm(-2)) illumination. The open-circuit voltage (V(OC) ≈ 0.85-0.87 V) is one of the highest values reported thus far for thiophene-based polymers (e.g., poly(3-hexylthiophene) V(OC) ≈ 0.6 V). The inverted device also achieved a remarkable PCE compared to other devices based on low-band-gap polymers. Ideal film morphology with bicontinuous percolation pathways was expected from the atomic force microscopy (AFM) images, space-charge-limited current (SCLC) mobility, and selected-area electron-diffraction (SAED) measurements. This molecular design strategy is useful for achieving simple, processable, and planar donor-acceptor (D-A)-type low-band-gap polymers with a deep HOMO for applications in photovoltaic cells.

Quinoxaline–thiophene based thick photovoltaic devices with an efficiency of ∼8%

A series of difluoroquinoxaline–thiophene based reduced band gap polymers was designed and synthesized by considering non-covalent coulombic interactions in a polymeric main chain. The insertion of different numbers of thiophene moieties allows for the adjustment of the absorption range, frontier energy levels, crystalline self-organization, film morphology and the resulting photovoltaic properties. A thick blend film of poly(thiophene-alt-(2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline)) (PDFQx-T):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) showed a rough, inhomogeneous and largely phase-separated surface morphology compared to a typical film with ∼100 nm thickness. A similar trend was observed in the surface morphology of a poly(2,2′-bithiophene-alt-(2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline)) (PDFQx-2T) blend film, showing deteriorated photovoltaic properties with increasing film thickness. In contrast, poly(2,2′:5′,2′′-terthiophene-alt-2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline) (PDFQx-3T) had a similar blend film morphology for both thick and thin active layers, showing a homogeneous and smooth morphology with a face-on orientation and tight π–π stacking (d-spacing = 3.6 A). The optimized photovoltaic cell based on PDFQx-3T : PC71BM achieved a power conversion efficiency (PCE) of 8% with an open-circuit voltage of 0.74 V, a short-circuit current of 17.19 mA cm−2 and a fill factor of 0.63 at an active layer thickness of ∼270 nm. It is still a challenge to develop photovoltaic polymers which allow efficient charge transport and extraction at a device thickness of ∼300 nm. Fine-adjustment of intra- and interchain interactions must be considered carefully to achieve high device properties for thick devices without deterioration in the blend morphology and charge recombination. This high PCE at an active layer thickness of ∼300 nm may suggest great potential for the mass production of printed polymer solar cells via industrial solution processes.

High-efficiency photovoltaic cells with wide optical band gap polymers based on fluorinated phenylene-alkoxybenzothiadiazole

A series of semi-crystalline, wide band gap (WBG) photovoltaic polymers were synthesized with varying number and topology of fluorine substituents. To decrease intramolecular charge transfer and to modulate the resulting band gap of D–A type copolymers, electron-releasing alkoxy substituents were attached to electron-deficient benzothiadiazole (A) and electron-withdrawing fluorine atoms (0–4F) were substituted onto a 1,4-bis(thiophen-2-yl)benzene unit (D). Intra- and/or interchain noncovalent Coulombic interactions were also incorporated into the polymer backbone to promote planarity and crystalline intermolecular packing. The resulting optical band gap and the valence level were tuned to 1.93–2.15 eV and −5.37 to −5.67 eV, respectively, and strong interchain organization was observed by differential scanning calorimetry, high-resolution transmission electron microscopy and grazing incidence X-ray scattering measurements. The number of fluorine atoms and their position significantly influenced the photophysical, morphological and optoelectronic properties of bulk heterojunctions (BHJs) with these polymers. BHJ photovoltaic devices showed a high power conversion efficiency (PCE) of up to 9.8% with an open-circuit voltage of 0.94–1.03 V. To our knowledge, this PCE is one of the highest values for fullerene-based single BHJ devices with WBG polymers having a band gap of over 1.90 eV. A tandem solar cell was also demonstrated successfully to show a PCE of 10.3% by combining a diketopyrrolopyrrole-based low band gap polymer.

Straight chain D–A copolymers based on thienothiophene and benzothiadiazole for efficient polymer field effect transistors and photovoltaic cells

Three types of linear and planar-structured donor (D)–acceptor (A) type alternating copolymers were synthesized by incorporating intrachain noncovalent Coulombic interactions, based on thieno[3,2-b]thiophene and benzothiadiazole (BT) moieties. The chain linearity and fine adjustment of interchain organization by the incorporation of different numbers of electronegative fluorine atoms onto BT, significantly affected the frontier energy levels, film morphology, and the resulting charge transport properties. The semi-crystalline morphology and charge carrier transport properties were studied by grazing incidence wide-angle X-ray scattering and polymer field-effect transistor (PFET) characteristic measurements. A hole mobility as high as 0.1 cm2 V−1 s−1 in PFET was obtained for poly[2,5-bis(decyltetradecyloxy)benzene-alt-4,7-bis(thieno[3,2-b]thiophene)-5,6-difluoro-2,1,3-benzothiadiazole] (PPDTT2FBT), suggesting a strong self-organization due to the linear chain configuration with conformation lock. The difluorinated PPDTT2FBT also showed the highest power conversion efficiency (PCE, 6.4%) by blending with PC71BM, but a poorer photovoltaic performance was obtained compared to the wavy-structured counterpart, poly[2,5-bis(2-hexyldecyloxy)phenylene-alt-5,6-difluoro-4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole] (PPDT2FBT), reported previously. The mainly edge-on orientation of PPDTT2FBT (with π–π stacking in both xy and z directions) is attributed to the moderate PCE in the blends. Fine modulation of chain linearity may suggest an effective way to control the desirable interchain ordering and bulk film morphology for specific application in polymer solar cells or field effect transistors.

Amorphous Thieno[3,2-b]thiophene and Benzothiadiazole Based Copolymers for Organic Photovoltaics

Three types of amorphous thienothiophene (TT)-benzothiadiazole (BT) based copolymers (PFTTBT) were synthesized by incorporating alkyl-substituted fluorene moieties as a third component in the polymer backbone. Their optical, electrochemical, morphological, and photovoltaic properties were examined by a comparison with those of a crystalline TT-BT derivative (PTTBT14). PTTBT14 was reported to have a high hole mobility (0.26 cm(2)/(V s)) due to the pronounced interchain ordering but poor photovoltaic power conversion efficiency (PCE) of 2.4-2.6% was reported due to excessively strong self-interactions with poor miscibility with fullerene structures. By incorporating fluorene units, the UV-vis spectra showed an increased bandgap (∼1.9 eV) with the disappearance of the packing-originated shoulder peak, and the valence band decreased compared to crystalline PTTBT14. The amorphous PFTTBT polymers showed substantially improved photovoltaic properties compared to PTTBT14, even though they showed poor hole mobility (∼10(-6) cm2/(V s)) and fill factor. The optimal devices were achieved by blending with excess PC71BM (polymer:PC71BM=1:4 by weight), showing little improvement in the thermal and additive treatments. Under simulated solar illumination of AM 1.5 G, the best PCE of 6.6% was achieved for a PFehTTBT:PC71BM device with an open-circuit voltage of 0.92 V, a short-circuit current of 15.1 mA/cm2, and a fill factor of 0.48. These results suggest that it is useful to disrupt partially the interchain organizations of excessively crystalline polymers, enabling fine-control of intermolecular ordering and the morphological properties (i.e., miscibility with fullerene derivatives, etc.) to utilize the advantages of both crystalline and amorphous materials for further improving PCE of polymer solar cells.

Thienothiophene-benzotriazole-based semicrystalline linear copolymers for organic field effect transistors

Abstract A series of thienothiophene-benzotriazole-based semicrystalline copolymers, PTTBTz, PTTBTz-F, and PTTBTz-OR, were synthesized by considering chain linearity, planarity and inter-chain packing by virtue of non-covalent attractive interaction. Fluorine and alkoxy substituents were introduced to modulate the intra- and inter-chain coulombic interactions and crystalline ordering. The fluorine and alkoxy-substituted PTTBTz-F and PTTBTz-OR showed pronounced inter-chain packing with edge-on orientation confirmed by UV-vis absorption and X-ray diffraction measurements. The well-resolved diffraction patterns were obtained for PTTBTz-F and PTTBTz-OR, showing (100)∼(500) inter-lamellar scattering peaks (d-spacing, 17∼18 Å) in the out-of-plane direction and a π-π stacking peak (d-spacing, 3.5∼4.1 Å) in the in-plane direction. Organic field effect transistor (OFET) devices were fabricated with a bottom gate and top contact geometry. PTTBTz-F (μh = 4.49 × 10–2 cm2 V–1 s–1, on/off ratio = 1.13 × 107) and PTTBTz-OR (μh = 8.39 × 10–3 cm2 V–1 s–1, on/off ratio = 2.98 × 104) showed nearly 3 and 2 orders of magnitude higher hole mobility upon annealing at 305 and 260 °C, with compared to the unsubstituted PTTBTz.