NIR Electrofluorochromic Properties of Aza-Boron-dipyrromethene Dyes.

The photophysical properties of near-infrared (NIR) emissive aza-boron-dipyrromethene (aza-BDP) dyes incorporating nitrofluorene and alkoxy decorations were intensively investigated. Their highly reversible one-electron reduction process showed characteristic electrofluorochromic (EF) properties in the NIR range, depending on the substituents. The nitrofluorene ethynyl-substituted (Type I) dyes showed smaller EF effects than the alkoxy-containing (Type II) dyes because of the difference in their intrinsic fluorescence contrast between the neutral and reduced states (radical anion). In addition, the Type II chromophores showed a larger diffusion coefficient for ion transport, which enhanced the EF contrast and the response time for the fluorescence change at a given step potential. With an optimized condition, the NIR EF ON/OFF ratio reached a value of 6.1 and a long cyclability over 1000 EF cycles between -0.4 V and +0.4 V switching potentials, with approximately 20% loss of the initial ON/OFF switching ratio. The NIR EF switching was visually observed through a visible light cut-off filter, featuring high fluorescence contrast.

Photothermally Activated Pyroelectric Polymer Films for Harvesting of Solar Heat with a Hybrid Energy Cell Structure.

Photothermal effects in poly(3,4-ethylenedioxythiophene)s (PEDOTs) were explored for pyroelectric conversion. A poled ferroelectric film was coated on both sides with PEDOT via solution casting polymerization of EDOT, to give highly conductive and effective photothermal thin films of PEDOT. The PEDOT films not only provided heat source upon light exposure but worked as electrodes for the output energy from the pyroelectric layer in an energy harvester hybridized with a thermoelectric layer. Compared to a bare thermoelectric system under NIR irradiation, the photothermal-pyro-thermoelectric device showed more than 6 times higher thermoelectric output with the additional pyroelectric output. The photothermally driven pyroelectric harvesting film provided a very fast electric output with a high voltage output (Vout) of 15 V. The pyroelectric effect was significant due to the transparent and high photothermal PEDOT film, which could also work as an electrode. A hybrid energy harvester was assembled to enhance photoconversion efficiency (PCE) of a solar cell with a thermoelectric device operated by the photothermally generated heat. The PCE was increased more than 20% under sunlight irradiation (AM 1.5G) utilizing the transmitted light through the photovoltaic cell as a heat source that was converted into pyroelectric and thermoelectric output simultaneously from the high photothermal PEDOT electrodes. Overall, this work provides a dynamic and static hybrid energy cell to harvest solar energy in full spectral range and thermal energy, to allow solar powered switching of an electrochromic display.

PEDOT as a Flexible Organic Electrode for a Thin Film Acoustic Energy Harvester.

An efficient thin film acoustic energy harvester was explored using flexible poly(3,4-ethylene dioxythiophene) (PEDOT) films as electrodes in an all-organic triboelectric generator (AO-TEG). A thin film AO-TEG structured as PEDOT/Kapton//PET/PEDOT was prepared by the solution casting polymerization(SCP) on the dielectric polymer films. As-prepared AO-TEG showed high flexibility and durability due to the strong adhesion between the electrodes and the dielectric polymer. The short-circuit current density (Jsc), open-circuit voltage (Voc), and maximum power density (Pw) reached 50 mA/m(2), 700 V, and 12.9 W/m(2) respectively. The output current density decreased with the increase in the electrode resistance (Re), but the energy loss in the organic electrodes was negligible. The AO-TEG could light up 180 LEDs instantaneously upon touching of the AO-TEG with a palm (∼120 N). With the flexible structure, the AO-TEG was worn as clothes and generated electricity to light LEDs upon regular human movement. Furthermore, the AO-TEG was applicable as a thin film acoustic energy harvester, which used music to generate electricity enough for powering of 5 LEDs. An AO-TEG with a PEDOT electrode (Re = 200 Ω) showed instantaneous peak-to-peak voltage generation of 11 V under a sound pressure level (SPL) of 90-100 dB. The harvested acoustic energy through the AO-TEG was 350 µJ from the 4 min playing of the same single song. This is the first demonstration of a flexible triboelectric generator (TEG) using an organic electrode for harvesting acoustic energy from ambient environment.

Switchable silver mirrors with long memory effects.

An electrochemically stable and bistable switchable mirror was achieved for the first time by introducing (1) a thiol-modified indium tin oxide (ITO) electrode for the stabilization of the metallic film and (2) ionic liquids as an anion-blocking layer, to achieve a long memory effect. The growth of the metallic film was denser and faster at the thiol-modified ITO electrode than at a bare ITO electrode. The electrochemical stability of the metallic film on the thiol-modified ITO was enhanced, maintaining the metallic state without rupture. In the voltage-off state, the metal film maintained bistability for a long period (>2 h) when ionic liquids were introduced as electrolytes for the switchable mirror. The electrical double layer in the highly viscous ionic liquid electrolyte seemed to effectively form a barrier to the bromide ions, to protect the metal thin film from them when in the voltage-off state.

NIR-sensitive poly(3,4-ethylenedioxyselenophene) derivatives for transparent photo-thermo-electric converters.

Electrochromism, photothermal effect, and thermoelectric properties of hexyl-derivatized poly(3,4-ethylenedioxyselenophene) are investigated by precisely controlling the morphology. These properties are clearly demonstrated by controlling the applied electrical potential of the polymer films. Especially, the doped polymer film at -0.1 V reveals the highest photothermal conversion efficiency and a power factor of 42.5% and 354.7 µW m(-1) K(-2) , respectively. Efficient visible to near-infrared absorption, photon to heat, and heat to electric conversion has been realized in one film that could benefit in exploiting multifunctional film displays, invisible NIR sensors, photodynamic theragnosis, and thermoelectric devices.

Electroactive subwavelength gratings (ESWGs) from conjugated polymers for color and intensity modulation.

Subwavelength gratings with electroactive polymers such as poly(3-hexylthiophene) (P3HT) and poly(3,4-propylenedioxythiophene-phenylene) (P(ProDOT-Ph)) controlled the color intensity for various visible colors of diffracted light in a single device. Under the illumination of a white light, at a fixed angle of incidence, the color intensity of the diffracted light was reversibly switched from the maximum value down to 15% (85% decrease) by applying -2 to 2 V due to electrochemical (EC) reaction. All spectral colors including red, green, and blue were generated by changing the angle of incidence, and the intensity of each color was modulated electrochemically at a single EC device. With electroactive subwavelength gratings (ESWGs) of P3HT, the maximum modulation of the color intensity was observed in the red-yellow quadrant in the CIE color plot, whereas for the ESWGs of P(ProDOT-Ph), the maximum modulation of the color intensity was observed in the yellow-green and green-blue quadrants. Both ESWGs showed a memory effect, keeping their color and intensity even after power was turned off for longer than 40 hours.

Color combination of conductive polymers for black electrochromism.

Conducting polymers that absorb three primary colors, red, green, and blue (RGB), were introduced with a yellow electrochromic polymer (Y) for the preparation of black electrochromic devices. Red poly(3-hexylthiophene) (P3HT) and blue poly(3,4-ethylenedioxythiophene) (PEDOT) were coated on one side of the electrode as a cathodically coloring electrochromic (EC) layer, while green poly(aniline-N-butylsulfonate) (PANBS) and yellow EC poly{[1,3-bis(9',9'-dihexylfluoren-20-yl)azulenyl]-alt-[2",7"-(9",9"-dihexylfluorenyl]} (PDHFA) were coated on the opposite electrode to complete a complementary EC device. The yellow PDHFA layer effectively compensated for absorption below 450 nm and above the 600 nm region, which was lacking in the RGB electrode. The resultant RGBY ECD provided a black color near the CIE black with L*, a*, and b* values of 32, -1.1, and 3.7, respectively, covering a broad absorption in the visible range in the colored state. The state of the black EC device was maintained, even after the electricity was turned off for 200 h, showing stable memory effect.