Hwajeong Kim

Inverted polymer fullerene solar cells exceeding 10% efficiency with poly(2-ethyl-2-oxazoline) nanodots on electron-collecting buffer layers.

Polymer solar cells have been spotlighted due to their potential for low-cost manufacturing but their efficiency is still less than required for commercial application as lightweight/flexible modules. Forming a dipole layer at the electron-collecting interface has been suggested as one of the more attractive approaches for efficiency enhancement. However, only a few dipole layer material types have been reported so far, including only one non-ionic (charge neutral) polymer. Here we show that a further neutral polymer, namely poly(2-ethyl-2-oxazoline) (PEOz) can be successfully used as a dipole layer. Inclusion of a PEOz layer, in particular with a nanodot morphology, increases the effective work function at the electron-collecting interface within inverted solar cells and thermal annealing of PEOz layer leads to a state-of-the-art 10.74% efficiency for single-stack bulk heterojunction blend structures comprising poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] as donor and [6,6]-phenyl-C71-butyric acid methyl ester as acceptor.

Distorted Asymmetric Cubic Nanostructure of Soluble Fullerene Crystals in Efficient Polymer:Fullerene Solar Cells

We found that 1-(3-methoxycarbonyl)propyl-1-phenyl-(6,6)C(61) (PCBM) molecules make a distorted asymmetric body-centered cubic crystal nanostructure in the bulk heterojunction films of reigoregular poly(3-hexylthiophene) and PCBM. The wider angle of distortion in the PCBM nanocrystals was approximately 96 degrees , which can be assigned to the influence of the attached side group to the fullerene ball of PCBM to bestow solubility. Atom concentration analysis showed that after thermal annealing the PCBM nanocrystals do preferentially distribute above the layer of P3HT nanocrystals inside devices.

Organic solar cells based on conjugated polymers : History and recent advances

Organic solar cells have attracted huge attention because of their potential in the low-cost manufacturing of plastic solar modules featuring flexible, lightweight, ultrathin, rollable and bendable shapes. The power conversion efficiency of organic solar cells is now passing ~10%, which is a critical sign toward commercialization because organic solar cells surpass any other types of solar cells in terms of development speed. The encouraging efficiency enhancement could be realized by introducing a ‘bulk heterojunction’ concept that overcomes the weakness of organic semiconductors by minimizing their charge transport paths through making effective p-n junctions inside bulk organic films. However, there are several hurdles for commercialization, including stability and lifetime issues, owing to the bulk heterojunction concept. This review summarizes the important aspects of organic solar cells, particularly focusing on conjugated polymers as an active layer component.

Doping Effect of Organosulfonic Acid in Poly(3-hexylthiophene) Films for Organic Field-Effect Transistors

We attempted to dope poly(3-hexylthiophene) (P3HT) with 2-ethylbenzenesulfonic acid (EBSA), which has good solubility in organic solvents, in order to improve the performance of organic field effect transistors (OFET). The EBSA doping ratio was varied up to 1.0 wt % because the semiconducting property of P3HT could be lost by higher level doping. The doping reaction was confirmed by the emerged absorption peak at the wavelength of ~970 nm and the shifted S2p peak (X-ray photoelectron spectroscopy), while the ionization potential and nanostructure of P3HT films was slightly affected by the EBSA doping. Interestingly, the EBSA doping delivered significantly improved hole mobility because of the greatly enhanced drain current of OFETs by the presence of the permanently charged parts in the P3HT chains. The hole mobility after the EBSA doping was increased by the factor of 55-86 times depending on the regioregularity at the expense of low on/off ratio in the case of unoptimized devices, while the optimized devices showed ~10 times increased hole mobility by the 1.0 wt % EBSA doping with the greatly improved on/off ratio even though the source and drain electrodes were made using relatively cheaper silver instead of gold.

Organic phototransistors with nanoscale phase-separated polymer/polymer bulk heterojunction layers

Low-cost detectors for sensing photons at a low light intensity are of crucial importance in modern science. Phototransistors can deliver better signals of low-intensity light by electrical amplification, but conventional inorganic phototransistors have a limitation owing to their high temperature processes in vacuum. In this work, we demonstrate organic phototransistors with polymer/polymer bulk heterojunction blend films (mixtures of p-type and n-type semiconducting polymers), which can be fabricated by inexpensive solution processes at room temperature. The key idea here is to effectively exploit hole charges (from p-type polymer) as major signaling carriers by employing p-type transistor geometry, while the n-type polymer helps efficient charge separation from excitons generated by incoming photons. Results showed that the present organic transistors exhibited proper functions as p-type phototransistors with ∼4.3 A W(-1) responsivity at a low light intensity (1 µW cm(-2)), which supports their encouraging potential to replace conventional cooled charge coupled devices (CCD) for low-intensity light detection applications.

Polymer chain/nanocrystal ordering in thin films of regioregular poly(3- hexylthiophene) and blends with a soluble fullerene{

Here we report a study of the polymer chain/nanocrystal ordering in thin films (nanolayers) of regioregular poly(3-hexylthiophene) (P3HT) and blends of P3HT with a soluble fullerene derivative. A detailed analysis has been made of two dimensional (2D) grazing incidence X-ray diffraction (GIXRD) measurements with synchrotron radiation. P3HT samples with three different levels of regioregularity (RR) were synthesized and used to investigate the influence of RR on the chain ordering in thin films. Blend films were also prepared to investigate the influence of fullerene molecule addition on chain ordering. For the analysis, one dimensional (1D) GIXRD patterns were extracted from the 2D images for varying azimuthal angles, allowing information to be obtained for chain ordering in both the out-of-plane (OOP) and in-plane (IP) directions. These results show that the degree of P3HT chain ordering is strongly affected by RR, and that thermal annealing improves chain ordering in the OOP direction. This observation is in good agreement with high resolution transmission electron microscope measurements of film nanomorphology.

Temperature/time-dependent crystallization of polythiophene: fullerene bulk heterojunction films for polymer solar cells.

We report the temperature/time-dependent crystallization of poly(3-hexylthiophene) (P3HT) in blend films of P3HT and [6,6]-phenyl-C(61)-butyric acid methyl ester (PC₆₁BM). The crystallization behaviour of P3HT:PC₆₁BM blend films was measured as a function of annealing time at two different temperatures (150°C and 160°C) by employing a synchrotron-radiation grazing-incidence angle X-ray diffraction (GIXD) technique. The crystallization behaviour was correlated with corresponding solar cells annealed under the same conditions. Results showed that the trend of device performance was almost in accordance with that of the (100) GIXD intensity, indicating that the nanostructure change in blend films does affect the device performance. However, the intermediate zones related to nanomorphology fluctuations, which were observed for lower temperature (140°C) annealing, were significantly suppressed at higher temperature (150°C and 160°C) annealing.

Nanomorphology-driven two-stage hole mobility in blend films of regioregular and regiorandom polythiophenes

We report the nanomorphology-driven two-stage hole mobility in the blend films of regioregular and regiorandom poly(3-hexylthiophene) (P3HT) polymers of which regioregularity was 92.2% and 33.0%, respectively. The hole mobility of blend films was measured by employing a top-contact type organic field-effect transistor which has an aromatic polyimide gate insulating layer and silver source/drain electrodes. Results showed that the hole mobility of blend films was suddenly reduced as large as two orders of magnitude as the bulk regioregularity of blend films decreased from 89.8% to 86.3%, even though the hole mobility change was far less than one order of magnitude after and before this boundary condition. The discontinuous two-stage hole mobility trend has been attributed to the destruction of P3HT chain ordering/alignment in the blend films at the boundary blend composition, as evidenced from the huge changes in optical absorption coefficient, surface nanomorphology, and in-plane/out-of-plane nanostructures in the blend films.

Significant stability enhancement in high-efficiency polymer:fullerene bulk heterojunction solar cells by blocking ultraviolet photons from solar light

Achievement of extremely high stability for inverted‐type polymer:fullerene solar cells is reported, which have bulk heterojunction (BHJ) layers consisting of poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐3‐fluorothieno[3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM), by employing UV‐cut filter (UCF) that is mounted on the front of glass substrates. The UCF can block most of UV photons below 403 nm at the expense of ≈20% reduction in the total intensity of solar light. Results show that the PTB7‐Th:PC71BM solar cell with UCF exhibits extremely slow decay in power conversion efficiency (PCE) but a rapidly decayed PCE is measured for the device without UCF. The poor device stability without UCF is ascribed to the oxidative degradation of constituent materials in the BHJ layers, which give rise to the formation of PC71BM aggregates, as measured with high resolution and scanning transmission electron microscopy and X‐ray photoelectron spectroscopy. The device stability cannot be improved by simply inserting poly(ethylene imine) (PEI) interfacial layer without UCF, whereas the lifetime of the PEI‐inserted PTB7‐Th:PC71BM solar cells is significantly enhanced when UCF is attached.

Initial performance changes of polymer/fullerene solar cells by short-time exposure to simulated solar light.

Recently, polymer solar cells have attracted keen interest as sustainable energy conversion media owing to their potential for low-cost manufacturing and advanced features, including their semi-transparency and light-weight, ultrathin, and flexible form factors. These characteristics are expected to broaden the application of polymer solar cells towards mobile and/or consumer electronics; no longer limited to conventional solar power modules fixed to land installations and/or buildings. So far, the power conversion efficiency (PCE) of polymer solar cells has been gradually improved by controlling the nanomorphology of the active layer as well as by introducing new tailored polymer materials based on bandgap engineering. Recent reports have forecast that the PCE of polymer solar cells can reach 11–16 % via further bandgap engineering of semiconducting polymers and acceptor molecules. 13] However, in addition to enhancing the efficiency, the stability of polymer solar cells is a critical issue for their commercialization. To date, tens of reports on the stability and/or lifetime of polymer solar cells have appeared. These reports have shown the importance of encapsulation to avoid attack by oxygen, as well-documented in the study of organic light-emitting devices (OLEDs). The studies pay particular attention to the time-dependent decay of short-circuit current density (Jsc) and open-circuit voltage (Voc), in the presence of performance oscillation, in polymer solar cells and/or modules prepared using blend films of poly(3-hexylthiophene) (P3HT) and 1-(3methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM). [25] The parameters Jsc and Voc quickly degraded after about 200 h at 65 8C, whereas the fill factor (FF) increased up to 600 h. However, the initial quick drop in Jsc and Voc was not clearly addressed although it might be key to understanding the stability issues of polymer solar cells. Hence, in this work, we attempt to describe the initial performance changes in P3HT:PCBM solar cells during continuous illumination by simulated solar light. To concentrate on the very early stages of illumination, we collected device data every hour, from 0 to 11 h (the longest time here). To understand the performance changes, the blend films were analyzed by optical absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and phase-contrast atomic force microscopy (AFM) before and after illumination (11 h). Results and Discussion