Liquid crystalline semiconductor is an interesting category of organic electronic materials and also has been extensively studied in terms of "Printed Electronics". For the wider diversity in research toward new applications, one can consider how to use a combination of miscibility and phase separation in liquid crystals. Here we report discotic liquid crystals in making a composite of which structural order is controlled in nano-scale toward photovoltaic applications.
Discotic columnar LCs were studied on their resultant molecular order and carrier transport properties. Liquid crystals of phthalocyanine and its analogues which exhibit columnar mesomorphism with high carrier mobility (10-1 cm2/Vs) were examined with making binary phase diagrams and the correlation to carrier transport properties by TOF measurements was discussed. The shape-analogues in chemical structure shows a good miscibility even for the different lattice-type of columnar arrangement and the carrier mobility is mostly decrease except for a case of combination with a metal-free and the metal complex. For the mixtures with non-mesogenic C60 derivatives, one sees a phase-separated structure due to its immiscibility, though the columnar order is remained in a range of component ratio.Especially, in a range of the ratio, it was observed the phase separated C60 derivatives are fused into the matrix of columnar bundles, indicating C60 derivatives could be diffused in columnar arrays in molecular level.
The efficiency of the conduction of photocurrent in discotic liquid crystals is known to depend on the quality of the
columnar organization. Solvents have shown to be able to influence the formation of wire structures on substrates
promoting very long and ordered wired formations or bulkier structures depending on the affinity of the solvent with
parts of the molecular structure of discotics. Here we present a study on the effect of solvents when the liquid crystal is
confined between two substrates with the columns running perpendicular to them, geometry used in solar cells. We
focused on toluene and dodecane, solvents that have shown to promote on substrates the formation of aligned and long
nanowires and bulk large and isolated fibers, respectively. The phase transition behavior indicates that toluene does not
interfere with the columnar formation while dodecane strongly influence increasing the disorder in the structure.
Binary blends of phthalocyanine (Pc) LCs, 1, 4, 8, 11, 15, 18, 22, 25-octadecylphthalocyanine (C10PcH2) and the corresponding Zn complex (C10PcZn) were studied which have the identical hexagonal columnar (Colh) mesophase and the same order of carrier mobility (~ 10-1 cm2 V-1 s-1) in the mesophase. The phase diagram shows a complete miscibility in the Colh mesophase and no eutectic point was detected. The carrier mobility evaluated by Time-Of-flight (TOF) technique goes down to 10-2 cm2 V-1 s-1 in Colh phase of the initial blends prepared by solution mixing. However, the treatment of these binary systems with repetitive heating and cooling gives recovering of carrier mobility to the original level, though their HOMO and LUMO levels are slightly different in these two mesogenic Pcs. These results indicate that two types of single component column form a hexagonal array in mesophase. Also the blends with PCBM were studied on carrier mobility as well as miscibility and phase separation.
KEYWORDS: Solar cells, Heterojunctions, Photovoltaics, Thin film solar cells, External quantum efficiency, Absorbance, Crystals, Molecules, Absorption, Energy conversion efficiency
Bulk heterojunction organic thin-film solar cells utilizing soluble phthalocyanine derivatives, 1,4,8,11,15,18,22,25-octaalkylphthalocyanine (CnPcH2, n = 6, 7, 9, 10), were investigated. Two broad peaks existing in the external quantum efficiency spectra almost correspond to the Q-band and B-band of CnPcH2. The solar cell utilizing C6PcH2 had the best photovoltaic properties as evidenced by open-circuit voltage, short-circuit current density, fill factor, and energy conversion efficiency. Almost the same photovoltaic properties were observed in the solar cells utilizing C9PcH2 and C10PcH2. We discuss the photovoltaic properties by taking into consideration the crystal structure and electronic state of CnPcH2 from the results of the absorbance spectra, X-ray diffraction measurement, and polarization microscope observation.
Binary mixtures of a phthalocyanine (Pc) mesogen and its Zn complex, which have eight decyl chains at the nonperipheral
positions of Pc were studied as an organic semiconducting system. The complete miscibility was observed for
the Colh mesophase and the carrier mobility for the Colh mesophase was measured to give small decrease of mobility in
the 1:1 mixture in comparison to that of the pure compounds. These indicate that in this binary system, two compounds
could mostly behave as the identical molecules and no specific interaction was expected. The different component ratio
affects the carrier mobility depending on the ratio, meaning the molecular dispersion is not taken place in a monomolecular
level and possibly columns formed by each compound exist to hold a certain distance for successive charge
hopping. These results indicate that the mixture of mesogens could make mesogenic systems useful for new applications
such as organic thin film solar cells.
A liquid crystalline phthalocyanine semiconductor, 1, 4, 8, 11, 15, 18, 22, 25-hexahexylphthalocyanine (C6PcH2) was
studied on the drift mobility of charged carriers by a Time-Of-Flight (TOF) method. It was found that this compound
exhibits an ambipolar nature for charge transport and the hole and electron mobilities were determined to be in the order
of 10-1 cm2 V-1 s-1 for polydomain films of the hexagonal disordered columnar (Colhd) mesophase. This is comparable to
that of the octyl homologue (C8PcH2) reported by Hanna et al. However, C6PcH2 did not show any tendency to form the
homeotropic alignment between ITO-coated glass substrates, though C8PcH2 so clearly and easily does. Clear decay
curves of the transient photocurrents could be obtained in TOF measurements even for polydomain films of the
crystalline solid phase to give a strongly temperature-dependent mobility of holes which reaches to 1.1 cm2 V-1 s-1 at
room temperature (RT) as the temperature goes down, whilst the electron mobility slightly increases to be 0.5 cm2 V-1 s-1at RT. This compound could easily form thin films by spin-coating technique with the toluene solution and a simple
bulk-heterojunction thin film solar cell was fabricated to give a good performance such as 3.1 % of power conversion
efficiency and > 70 % of external quantum efficiency.
Here we show the simple fabrication of field effect transistor (FET) with a mesophase semiconductor, a derivative of
dithienyl naphthalene, which exhibits a fast mobility (10-1 ~ 10-2 cm2 V-1 s-1) of charged carriers in the mesophase. The
compound is a mesogen, but with highly ordered layered structure in a triclinic lattice, meaning a 3D-mesophase is
formed. The device performance was studied for the transistor mobility, on/off ratio and threshold voltage of device
operation, to have 0.14 cm2 V-1 s-1, 2 x 103 and -27 V at room temperature (in a crystal phase), respectively, even though
the thin film active layer (100 nm thick) does have a multi-domain system. However, the XRD studies indicate the
uniformly aligned molecules in each domain, of which long axis is inclined to be ca. 27° against the axis perpendicular
to the substrate plane. This implies that a self-assembling nature of mesogenic molecules is a certain merit for thin film
device fabrication in organic electronics.
A new phenomenon was found for the alignment change of hexagonal columnar (Colh) mesophase of a typical discotic liquid crystal of triphenylene derivatives, which is caused by a polarizing infrared laser irradiation with a wavelength to excite the vibrational mode of the selected chemical bond in the mesogen. A series of experiments has revealed that the polarization direction of incident laser is correlated to the molecular alignment generated by the irradiation, where the molecules are reoriented in a way that the molecules no longer absorb the incidence. The resultant new domain has a certain level of uniformity for the alignment from an optical point of view and remains for several hours to minutes depending on the temperature against the isotoropization. The manual scanning of the beam successfully gives uniform domains with a shape and one can generate a character "H", for example, with lath-like shaped uniform domains in the mesophase film. It was found that such new domains could be freezed into the polymer film by photopolymerization when the mesogens have polymerizable groups in the molecular flamework. This strongly indicate that the combination of the infrared control of the molecular alignment of Colh mesophase and the following photopolymerization could realize highly functional polymer films where the structured domains with a variety of shapes and alignments are assembled in the film. Recently, it was also demonstrated that a homeotropic domain could be generated using a circularly polarized incidence at 6.18 μm which corresponds to the wavelength to excite the aromatic C-C stretching band, being coincident with the relation of the alignment to the polarization direction of incidence.
A mesomorphic long-chain tetraphenylporphyrin was investigated on the visible absorption and fluorescence spectra and the fluorescence lifetime was measured through the phase transitions. All results indicate that the low- temperature lamellar mesophase has face-to-face molecular arrangement, through the high-temperature one does not as the proposed structures based on the powder x-ray diffraction studies.
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