We report photovoltaic devices consisting of patterned TiO2, porphyrin dyes, and layer‐by‐layer (LBL) polyelectrolyte multilayer/oligoethylene glycol dicarboxylic acid (OEGDA) composite films. A composite polyelectrolyte LBL/OEGDA film was fabricated by formation of an alternating multilayer of linear polyethyleneimine (LPEI) and polyacrylic acid (PAA), followed by immersion of the LBL film into an OEGDA aqueous solution. The ionic conductivity attained in this LBL LPEI/PAA and OEGDA composite film was approximately 10–5 S cm–1 at room temperature and humidity. Investigations of dye‐sensitized photovoltaic devices constructed with the LBL (LPEI/PAA)/OEGDA composite films, TiO2, and four types of porphyrin dyes resulted in optimization of the dye molecule and its orientation at the interface with the ionically conductive composite. The photocurrent value of photovoltaic devices constructed with the composite LBL/OEGDA film from illumination of a xenon white light source exhibited a nearly 1.5 times enhancement over the device without OEGDA. This enhancement of the photocurrent was due to the high room‐temperature ionic conductivity of the multilayer composite film. Further marked improvements of the photovoltaic performance were achieved by patterning the TiO2 electrode using polymer stamping as a template for TiO2 deposition. The device with patterned TiO2 electrodes exhibited almost 10 times larger conversion efficiencies than a similar device without patterning.
Electron drift mobility in pyrazolo[3,4-b]quinoline doped polystyrene layers
A novel solid-state polymer electrolyte was constructed using layer-by-layer (LbL) polyelectrolyte assembly of linear poly(ethylenimine) (LPEI) and poly(acrylic acid) (PAA), combined with a plasticization step using oligoethylene glycol dicarboxylic acid (OEGDA). This composite film exhibits a relatively high ionic conductivity of 9.5 x 10(-5) S/cm at 25 degrees C and 22% relative humidity. Detailed characterization of the composite was undertaken using grazing-angle Fourier transform infrared (GA-FTIR), atomic force microscopy (AFM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and impedance spectroscopy. After immersing the LPEI/PAA films into OEGDA aqueous solutions, the films exhibited a swelling behavior and increased surface roughness indicative of porosity induced by reorganization of ionic interactions between LPEI and PAA in acidic solution. This internal porous structure allows inclusion of OEGDA within the multilayer and increased ionic conductivity under ambient conditions due to the combined effects of plasticization of the LbL matrix by atmospheric water as well as the added mobility of ions in molten OEGDA within the composite.
Electrically pumped light emission was observed from a smectic mesophase of liquid-crystalline oxadiazole; 2,5-hexyloxybiphenyl–hexyloxyphenyl–oxadiazole (HOBP-OXD), which exhibits high electron transport capability. The light-emitting diode consisted of the HOBP-OXD film, a copper phthalocyanine vacuum deposited film as a hole injection layer, and a tris-(8-hydroxyquinoline) aluminum vacuum deposited film as an electron injection layer. The emission was linearly polarized originating from highly oriented molecular textures in the smectic mesophase with a degree of orientational order of 0.32.
The polymer-on-polymer stamping technique was used to template patterned TiO2 onto polymer thin films. Polystyrene-b-polyvinyl pyridine diblock copolymer (PS-b-PVP) was stamped on a layer-by-layer assembled thin film of poly(allylamine hydrochloride) and poly(acrylic acid). After rinsing the surface with a good solvent for the block copolymer, an adsorbed PS-b-PVP monolayer remained on the polyelectrolyte film, resulting in a pattern of alternating hydrophobic and carboxylic acid containing hydrophilic regions. The surface was used as a template for the selective deposition of TiO2 on the multilayer surface, using an acid-catalyzed hydrolysis of(NH4)2TiF6. Using this novel approach, we have successfully demonstrated the patterning of TiO2 film on a polyelectrolyte multilayer. Finally, nanoscale features consisting of 200 nm lines alternating with a 350 nm period was accomplished. This paper represents the first such attempt to create an all-polymer nonlithographic template for the directed deposition of TiO2 or related metal oxides; this technique, which utilizes the versatile polyelectrolyte multilayer process, enables the construction of complex polymer-inorganic microstructures suitable for electrooptical and photonic applications.
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