Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers.

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180(°).

Hybrid phototransistors based on bulk heterojunction films of poly(3-hexylthiophene) and zinc oxide nanoparticle.

Hybrid phototransistors (HPTRs) were fabricated on glass substrates using organic/inorganic hybrid bulk heterojunction films of p-type poly(3-hexylthiophene) (P3HT) and n-type zinc oxide nanoparticles (ZnO(NP)). The content of ZnO(NP) was varied up to 50 wt % in order to understand the composition effect of ZnO(NP) on the performance of HPTRs. The morphology and nanostructure of the P3HT:ZnO(NP) films was examined by employing high resolution electron microscopes and synchrotron radiation grazing angle X-ray diffraction system. The incident light intensity (P(IN)) was varied up to 43.6 µW/cm², whereas three major wavelengths (525 nm, 555 nm, 605 nm) corresponded to the optical absorption of P3HT were applied. Results showed that the present HPTRs showed typical p-type transistor performance even though the n-type ZnO(NP) content increased up to 50 wt %. The highest transistor performance was obtained at 50 wt %, whereas the lowest performance was measured at 23 wt % because of the immature bulk heterojunction morphology. The drain current (I(D)) was proportionally increased with P(IN) due to the photocurrent generation in addition to the field-effect current. The highest apparent and corrected responsivities (R(A) = 4.7 A/W and R(C) = 2.07 A/W) were achieved for the HPTR with the P3HT:ZnO(NP) film (50 wt % ZnO(NP)) at P(IN) = 0.27 µW/cm² (555 nm).

A pronounced dispersion effect of crystalline silicon nanoparticles on the performance and stability of polymer:fullerene solar cells.

We investigated the dispersion effect of crystalline silicon nanoparticles (SiNP) on the performance and stability of organic solar cells with the bulk heterojunction (BHJ) films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(61)BM). To improve the dispersion of SiNP in the BHJ films, we attached octanoic acid (OA) to the SiNP surface via esterification reaction and characterized it with Raman spectroscopy and high-resolution transmission electron microscopy. The OA-attached SiNP (SiNP-OA) showed improved dispersion in chlorobenzene without change of optical absorption, ionization potential and crystal nanostructure of SiNP. The device performance was significantly deteriorated upon high loading of SiNP (10 wt %), whereas relatively good performance was maintained without large degradation in the case of SiNP-OA. Compared to the control device (P3HT:PC(61)BM), the device performance was improved by adding 2 wt % SiNP-OA, but it was degraded by adding 2 wt % SiNP. In particular, the device stability (lifetime under short time exposure to 1 sun condition) was improved by adding 2 wt % SiNP-OA even though it became significantly decreased by adding 2 wt % SiNP. This result suggests that the dispersion of nanoparticles greatly affects the device performance and stability (lifetime).

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.

Device performance and lifetime of polymer:fullerene solar cells with UV-ozone-irradiated hole-collecting buffer layers.

We report the influence of UV-ozone irradiation of the hole-collecting buffer layers on the performance and lifetime of polymer:fullerene solar cells. UV-ozone irradiation was targeted at the surface of the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layers by varying the irradiation time up to 600 s. The change of the surface characteristics in the PEDOT:PSS after UV-ozone irradiation was measured by employing optical absorption spectroscopy, photoelectron yield spectroscopy, and contact angle measurements, while Raman and X-ray photoelectron spectroscopy techniques were introduced for more microscopic analysis. Results showed that the UV-ozone irradiation changed the chemical structure/composition of the surface of the PEDOT:PSS layers leading to the gradual increase of ionization potential with irradiation time in the presence of up-and-down variations in the contact angle (polarity). This surface property change was attributed to the formation of oxidative components, as evidenced by XPS and Auger electron images, which affected the sheet resistance of the PEDOT:PSS layers. Interestingly, device performance was slightly improved by short irradiation (up to 10 s), whereas it was gradually decreased by further irradiation. The short-duration illumination test showed that the lifetime of solar cells with the UV-ozone irradiated PEDOT:PSS layer was improved due to the protective role of the oxidative components formed upon UV-ozone irradiation against the attack of sulfonic acid groups in the PEDOT:PSS layer to the active layer.

Diimide nanoclusters play hole trapping and electron injection roles in organic light-emitting devices.

We report thermally stable diimide nanoclusters that could potentially replace the conventional thick electron transport layer (ETL) in organic light-emitting devices (OLEDs). Bis-[1,10]phenanthrolin-5-yl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic diimide (Bphen-BCDI) was synthesized from the corresponding dianhydride and amine moieties, and its purified product exhibited a high glass transition temperature (232 °C) and a wide band gap (3.8 eV). The Bphen-BCDI subnanolayers deposited on substrates were found to form organic nanoclusters, not a conventional layer. The OLED made with a subnanolayer of Bphen-BCDI nanoclusters, instead of a conventional ETL, showed greatly improved efficiency (about 2-fold) compared with an OLED without the diimide nanoclusters. The role of the BPhen-BCDI nanoclusters was assigned to hole trapping and electron injection in the present OLED structure.