Hyunbum Kang

Flexible, highly efficient all-polymer solar cells.

All-polymer solar cells have shown great potential as flexible and portable power generators. These devices should offer good mechanical endurance with high power-conversion efficiency for viability in commercial applications. In this work, we develop highly efficient and mechanically robust all-polymer solar cells that are based on the PBDTTTPD polymer donor and the P(NDI2HD-T) polymer acceptor. These systems exhibit high power-conversion efficiency of 6.64%. Also, the proposed all-polymer solar cells have even better performance than the control polymer-fullerene devices with phenyl-C61-butyric acid methyl ester (PCBM) as the electron acceptor (6.12%). More importantly, our all-polymer solar cells exhibit dramatically enhanced strength and flexibility compared with polymer/PCBM devices, with 60- and 470-fold improvements in elongation at break and toughness, respectively. The superior mechanical properties of all-polymer solar cells afford greater tolerance to severe deformations than conventional polymer-fullerene solar cells, making them much better candidates for applications in flexible and portable devices.

High‐Performance All‐Polymer Solar Cells Via Side‐Chain Engineering of the Polymer Acceptor: The Importance of the Polymer Packing Structure and the Nanoscale Blend Morphology

The effectiveness of side-chain engineering is demonstrated to produce highly efficient all-polymer solar cells (efficiency of 5.96%) using a series of naphthalene diimide-based polymer acceptors with controlled side chains. The dramatic changes in the polymer packing, blend morphology, and electron mobility of all-polymer solar cells elucidate clear trends in the photovoltaic performances.

Controlling Number of Indene Solubilizing Groups in Multiadduct Fullerenes for Tuning Optoelectronic Properties and Open-Circuit Voltage in Organic Solar Cells

The ability to tune the lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) levels of fullerene derivatives used as electron acceptors is crucial in controlling the optical/electrochemical properties of these materials and the open circuit voltage (V(oc)) of solar cells. Here, we report a series of indene fullerene multiadducts (ICMA, ICBA, and ICTA) in which different numbers of indene solubilizing groups are attached to the fullerene molecule. The addition of indene units to fullerene raised its LUMO and HOMO levels, resulting in higher V(oc) values in the photovoltaic device. Bulk-heterojunction (BHJ) solar cells fabricated from poly(3-hexylthiophene) (P3HT) and a series of fullerene multiadducts-ICMA, ICBA, and ICTA showed V(oc) values of 0.65, 0.83, and 0.92 V, respectively. Despite demonstrating the highest V(oc) value, the P3HT:ICTA device exhibited lower efficiency (1.56%) than the P3HT:ICBA device (5.26%) because of its lower fill factor and current. This result could be explained by the lower light absorption and electron mobility of the P3HT:ICTA device, suggesting that there is an optimal number of the solubilizing group that can be added to the fullerene molecule. The effects of the addition of solubilizing groups on the optoelectrical properties of fullerene derivatives were carefully investigated to elucidate the molecular structure-device function relationship.

Architectural Engineering of Rod–Coil Compatibilizers for Producing Mechanically and Thermally Stable Polymer Solar Cells

While most high-efficiency polymer solar cells (PSCs) are made of bulk heterojunction (BHJ) blends of conjugated polymers and fullerene derivatives, they have a significant morphological instability issue against mechanical and thermal stress. Herein, we developed an architecturally engineered compatibilizer, poly(3-hexylthiophene)-graft-poly(2-vinylpyridine) (P3HT-g-P2VP), that effectively modifies the sharp interface of a BHJ layer composed of a P3HT donor and various fullerene acceptors, resulting in a dramatic enhancement of mechanical and thermal stabilities. We directly measured the mechanical properties of active layer thin films without a supporting substrate by floating a thin film on water, and the enhancement of mechanical stability without loss of the electronic functions of PSCs was successfully demonstrated. Supramolecular interactions between the P2VP of the P3HT-g-P2VP polymers and the fullerenes generated their universal use as compatibilizers regardless of the type of fullerene acceptors, including mono- and bis-adduct fullerenes, while maintaining their high device efficiency. Most importantly, the P3HT-g-P2VP copolymer had better compatibilizing efficiency than linear type P3HT-b-P2VP with much enhanced mechanical and thermal stabilities. The graft architecture promotes preferential segregation at the interface, resulting in broader interfacial width and lower interfacial tension as supported by molecular dynamics simulations.

Effect of Fullerene Tris-adducts on the Photovoltaic Performance of P3HT:Fullerene Ternary Blends

Fullerene tris-adducts have the potential of achieving high open-circuit voltages (V(OC)) in bulk heterojunction (BHJ) polymer solar cells (PSCs), because their lowest unoccupied molecular orbital (LUMO) level is higher than those of fullerene mono- and bis-adducts. However, no successful examples of the use of fullerene tris-adducts as electron acceptors have been reported. Herein, we developed a ternary-blend approach for the use of fullerene tris-adducts to fully exploit the merit of their high LUMO level. The compound o-xylenyl C60 tris-adduct (OXCTA) was used as a ternary acceptor in the model system of poly(3-hexylthiophene) (P3HT) as the electron donor and the two soluble fullerene acceptors of OXCTA and fullerene monoadduct (o-xylenyl C60 monoadduct (OXCMA), phenyl C61-butyric acid methyl ester (PCBM), or indene-C60 monoadduct (ICMA)). To explore the effect of OXCTA in ternary-blend PSC devices, the photovoltaic behavior of the device was investigated in terms of the weight fraction of OXCTA (W(OXCTA)). When W(OXCTA) is small (<0.3), OXCTA can generate a synergistic bridging effect between P3HT and the fullerene monoadduct, leading to simultaneous enhancement in both V(OC) and short-circuit current (J(SC)). For example, the ternary PSC devices of P3HT:(OXCMA:OXCTA) with W(OXCTA) of 0.1 and 0.3 exhibited power-conversion efficiencies (PCEs) of 3.91% and 3.96%, respectively, which were significantly higher than the 3.61% provided by the P3HT:OXCMA device. Interestingly, for W(OXCTA) > 0.7, both V(OC) and PCE of the ternary-blend PSCs exhibited nonlinear compositional dependence on W(OXCTA). We noted that the nonlinear compositional trend of P3HT:(OXCMA:OXCTA) was significantly different from that of P3HT:(OXCMA:o-xylenyl C60 bis-adduct (OXCBA)) ternary-blend PSC devices. The fundamental reasons for the differences between the photovoltaic trends of the two different ternary-blend systems were investigated systemically by comparing their optical, electrical, and morphological properties.

Influence of intermolecular interactions of electron donating small molecules on their molecular packing and performance in organic electronic devices

Intermolecular interactions have a critical role in determining the molecular packing and orientation of conjugated polymers and organic molecules, leading to significant changes in their electrical and optical properties. Herein, we investigated the effects of intermolecular interactions of electron-donating small molecules on their structural, optical, and electrical properties, as well as on their performance in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). A series of dithienosilole-based small molecule donors were synthesized by introducing different terminal groups of ester and amide groups combined with three different versions of alkyl side chains. In comparison to dithienosilole-based small molecules with ester terminal groups, those with amide terminal groups exhibit strong intermolecular interaction by hydrogen bonding in a non-destructive manner. In addition, in order to control the intermolecular distance during assembly and thus fine-tune the interaction between the small molecule donors, three different alkyl side chains (i.e., n-octyl, n-decyl, and 2-ethylhexyl chains) were introduced into both small molecules with amide and ester terminal groups. The molecular packing and orientation of the small molecule donors were dramatically changed upon modifying the terminal groups and the alkyl side chains, as evidenced by grazing incidence X-ray scattering (GIXS) measurements. This feature significantly affected the electrical properties of the small molecules in OFETs. The trends in the activation energies for charge transport and the hole mobilities in OFETs were consistent with the molecular ordering and orientation propensity. In addition, the nano-scale morphology of small molecules blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was also influenced by the intermolecular interaction of small molecule donors. Power conversion efficiencies of more than 4.3% in OPVs were obtained from dithienosilole-based small molecules with ester terminal groups and linear side chains due to the optimized intermolecular interaction and morphology of the active layer.

The effect of side-chain length on regioregular poly[3-(4-n-alkyl)phenylthiophene]/PCBM and ICBA polymer solar cells

The photovoltaic, charge transport, light absorption and morphology properties of a series of poly[3-(4-n-alkyl)phenylthiophene] (PAPT):acceptor (phenyl-C61-butyric acid methyl ester (PCBM) or indene-C60 bisadduct (ICBA)) blend films are reported as a function of alkyl side-chain length. Regioregular poly[3-(4-n-butyl)phenylthiophene] (PBPT), poly[3-(4-n-hexyl)phenylthiophene] (PHPT), poly[3-(4-n-octyl)phenylthiophene] (POPT), and poly[3-(4-n-decyl)phenylthiophene] (PDPT) were successfully synthesized by a modified Grignard metathesis (GRIM) polymerization method. The effects of the alkyl side-chain length on the optical, electrochemical and structural properties of the polymers were carefully investigated to establish a relationship between the molecular structure and device function. Bulk heterojunction solar cells made of PAPTs blended with either PCBM or ICBA showed a strong photovoltaic property dependence on the alkyl side-chain length. Among all PAPTs used in this study, the best performance was observed in PHPT-based devices. This is the first report of the use of PHPT in polymer solar cells. In addition, PAPT devices blended with ICBA generally showed higher open-circuit voltages (Voc) and power conversion efficiencies than PCBM-based devices. For example, a PHPT:ICBA photovoltaic device showed a Voc of 0.79 V and a power conversion efficiency of 3.7%, which is the highest performance reported thus far using PAPT polymers. While the optical properties of PAPT/electron acceptor films exhibit the strongest effect on the short-circuit current of the devices, a balance between the optical, electrical and morphological properties of blended films caused by the alkyl side-chain length determines the overall photovoltaic performance of these devices. Therefore, our work provides a fundamental understanding of the molecular structure–device function relationship, especially with respect to changes in the alkyl side-chain length in conjugated polymers.

Controlling side-chain density of electron donating polymers for improving their packing structure and photovoltaic performance

A simple and efficient approach of controlling the side-chain density in the electron donating polymers has been demonstrated to tune their 3-D packing structure and HOMO level, which increases the hole mobility and V(oc) values, thus improving the solar cell performance.

Au@polymer core-shell nanoparticles for simultaneously enhancing efficiency and ambient stability of organic optoelectronic devices.

In this paper, we report and discuss our successful synthesis of monodispersed, polystyrene-coated gold core-shell nanoparticles (Au@PS NPs) for use in highly efficient, air-stable, organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs). These core-shell NPs retain the dual functions of (1) the plasmonic effect of the Au core and (2) the stability and solvent resistance of the cross-linked PS shell. The monodispersed Au@PS NPs were incorporated into a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film that was located between the ITO substrate and the emitting layer (or active layer) in the devices. The incorporation of the Au@PS NPs provided remarkable improvements in the performances of both OLEDs and OPVs, which benefitted from the plasmonic effect of the Au@PS NPs. The OLED device with the Au@PS NPs achieved an enhancement of the current efficiency that was 42% greater than that of the control device. In addition, the power conversion efficiency was increased from 7.6% to 8.4% in PTB7:PC71BM-based OPVs when the Au@PS NPs were embedded. Direct evidence of the plasmonic effect on optical enhancement of the device was provided by near-field scanning optical microscopy measurements. More importantly, the Au@PS NPs induced a remarkable and simultaneous improvement in the stabilities of the OLED and OPV devices by reducing the acidic and hygroscopic properties of the PEDOT:PSS layer.

Naphthalene-, Anthracene-, and Pyrene-Substituted Fullerene Derivatives as Electron Acceptors in Polymer-based Solar Cells

A series of aryl-substituted fullerene derivatives were prepared in which the aromatic moiety of [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) was modified by replacing the monocyclic phenyl ring with bicyclic naphthalene (NC61BM), tricyclic anthracene (AC61BM), and tetracyclic pyrene (PyC61BM). The PC61BM derivatives were synthesized from C60 using tosylhydrazone and were tested as electron acceptors in poly(3-hexylthiophene) (P3HT)-based organic photovoltaic cells (OPVs). The lowest unoccupied molecular orbital (LUMO) energy level of NC61BM (-3.68 eV) was found to be slightly higher than those of PC61BM (-3.70 eV), AC61BM (-3.75 eV), and PyC61BM (-3.72 eV). The electron mobility values obtained for the P3HT:PC61BM, P3HT:NC61BM, P3HT:AC61BM, and P3HT:PyC61BM blend films were 2.39 × 10(-4), 2.27 × 10(-4), 1.75 × 10(-4), and 2.13 × 10(-4) cm(2) V(-1) s(-1), respectively. P3HT-based bulk-heterojunction (BHJ) solar cells were fabricated using NC61BM, AC61BM, and PyC61BM as electron acceptors, and their performances were compared with that of the device fabricated using PC61BM. The highest power conversion efficiencies (PCEs) observed for devices fabricated with PC61BM, NC61BM, AC61BM, and PyC61BM were 3.80, 4.09, 1.14, and 1.95%, respectively, suggesting NC61BM as a promising electron acceptor for OPVs.