Design, Synthesis And Semiconductor Properties Of The Bipolar Based On Phthalocyanine Complexes

Organic semiconductors have attracted significant research interest for several decades due to these materials can potentially be fabricated very low cost, flexible and large-area organic electronic devices. O ne of the special attractions is that it largely depends on the nature of peripheral substitution groups and ring centre metal ions from Phthalocyanine or porphyrin as macrocyclic conjugated system. It is limited for their applications due to poor solubility and easy to accumulate in the solution for unsubstituents of phthalocyanine or porphyrin. So it is feasible to adjust the HOMO and LUMO energy levels of phthalocyanine or porphyrin by changing various peripheral substituents. Recently, owing to the unique electrical, optical and magnetic properties, associated with the intriguing intramolecular interactions, porphyrin, phthalocyanine and their derivatives have been the focus of the most intensively studied small molecule organic semiconductor and gas sensor devices.Our research work is focused on design and synthesis of novel molecules there physicochemical properties, the self-assembly of the materials and the applications of electronics functionality.? Amphiphilic Unsymmetrically-Substituted Porphyrin Zinc Derivatives: Synthesis, Aggregation Behavior in the Self-Assemblied Films and NO₂ Sensing PropertiesTwo novel amphiphilic porphyrin derivatives 5-?Benzo-?4-?2-?2-hydroxy?ethoxy?ethoxy??-10,15,20-triphenylporphyrinato zinc complex [ZnT?OC₂H₄OC₂H₄OH?PP]?1? and 5-(Benzo-?4-?2-?4,10-N,N-15-Crown-5?ethoxy??-10,15,20-triphenylporphyrinato zinc complex [ZnT(OC₂H₄NN₁₅C₅)PP]?2? were designed, synthesized, and characterized by a range of spectroscopic methods. Their electrochemistry has been studied by differential pulse voltammetry?DPV?. Highly ordered films of 1 and 2 were fabricated by a solution-based quasi- Langmuir-Sh?fer?Q LS? technique, and were characterized by electronic absorption spectra, IR, X-ray diffraction, atomic force microscopy?AFM? and current-voltage?I-V? measurements. Experimental results revealed that J-type aggregates have been formed in the QLS film of 1 and 2. The film crystallinity and general molecular order in the film of 1 are improved effectively in comparison with those of 2 due to the stronger intermolecular interactions in the film of 1. Furthermore, the conductivity of the QLS film of 1 was approximately 1 order of magnitude larger than that of 2, indicating significant effect of peripheral groups on conducting behavior of porphyrins. Moreover, the gas sensing behavior of the Q LS films of 1 and 2 toward electron acceptor gas, NO₂, was investigated in the concentrations of 200 and 800 ppm, respectively. The response sensitivity, stability, reproducibility follows the order 1 > 2, revealing the effect of the intermolecular interaction, film structure/morphology, and low- lying LUMO energy level on sensing performance. Unexpectedly, a decreased current response towards NO₂ for the Q LS films of both 1 and 2 were obtained for the first time, which unambiguously demonstrated the n-type semiconducting nature for 1 and 2. The present result represents not only the first example of n-type metalloporphyrin-based thin solid films obtained by a solution-based method, but more importantly provides an efficient way to enhance the performance of n-channel organic semiconductors through the combination of molecular design and film fabrication technique.? Controlled preparation of ZnS nanoparticle arrays in Langmiur monolayer of an unsymmetrical phthalocyaninato zinc complex: Synthesis, organization, and semiconducting propertiesA new unsymmetrical phthalocyaninato zinc complex with typical amphiphilic nature, namely 2,3-di?4- hydroxyphenoxy?-9,10,16,17,24,25-hexakis?n-octyloxy? phthalocyaninato zinc, Zn[Pc(OC₈H₁₇)₆?OPhOH?₂], has been designed, synthesized, and characterized by a range of spectroscopic methods. The Langmuir monolayer of this amphiphilic complex has been used as not only an organic template but also the good functional organic material to produce the monodispersed nanoparticles of Zn[Pc(OC₈H₁₇)₆?OPhOH?₂]/ZnS nanocomposite. In addition, multilayer pure and hybrid films have also been obtained by depositing monolayers of the amphiphilic complex and Zn[Pc(OC₈H₁₇)₆?OPhOH?₂]/ZnS nanocomposite, respectively, using the Langmuir-Sh?fer?LS? method. Surface pressure-area isotherms, UV- vis spectroscopic, and XRD studies indicate that the Zn[Pc(OC₈H₁₇)₆(OPhO] molecules adopted a face-to-face configuration and edge-on orientation in both the multilayer pure LS and Zn[Pc(OC₈H₁₇)₆?OPhOH?₂]/ZnS hybrid films. In particular, current-voltage?I-V? measurements reveal the significantly enhanced conductivity of the Zn[Pc(OC₈H₁₇)₆?OPhOH?₂]/ZnS hybrid film nanocomposites over the individual component ones due to the existence of the densely packed molecular architecture in the film matrix and the large interfacial area between the two components that removes the charge transporting bottleneck by creating an interpenetrating consistent thin film of the hybrid materials, indicating the potential of the present method in providing organic-inorganic hybrid nanostructures with good semiconducting properties.? Synthesis of two kinds of structurally similar Phthalocyaninato CopperAs one of the typical representatives of the functional molecular materials with large conjugated electronic molecular structure, phthalocyanines have been widely applied in flexible display and active- matrix electronic paper as well as smart cards in low-cost memory devices due to their unique optical, electrical, and magnetic properties. But the solubility of unsubstituent copper phthalocyanine is poor, which greatly limits its application. So we can introduce different substituents in the phthalocyanine to improve the solubility successfully.