Synthesis,property Research Of Phthalo-cyanine N-type Semiconductor Materials

Organic thin film transistor(OTFT)has been the focus of the organic photovoltaic field in recent years,due to the advantanges of simple fabrication process,low cost,good flexibility and large-scaled integration etc.Organic semiconductor material is an important part of the OFETs,and directly affect the mobility of organic thin film transistor devices.So far,the study of organic semiconductor materials are mostly the p-type materials,while n-type materials are relatively rare.In addition,the n-type organic semiconductor material is the important part of the bipolar transistor,p-n junction diode and complementary CMOS circuit.Therefore,the development of n-type organic semiconductor materials is of great significance to the OFETs devices research.?-electron conjugated system,good thermal stability performance and characteristics of vacuum evaporation film made phthalocyanine and subphthalocyanines compounds good semiconductor materials to prepare organic thin film transistor.In this article,first,the tetrafluorophthalonitrile was synthesized using tetrafluorophthalic anhydride as the raw material by imidization,ammonification and dehydration reaction and the synthetic process is optimized;second,using the tetrafluorophthalonitrile as the raw material synthesized 3 metal hexadecafluorophthalocyanines MPcF16(M = Cu,Zn,VO),the production rates were respectively 52.46 %,48.00 % and 14.90 %;next,3 dodecafluorosubphthalocyanines X-Bsub PcF12(X = Br,Cl,F)were prepared by the tetrafluorophthalonitrile,the production rates were respectively 30.01 %,33.98 % and 28.57 %;then using the phthalonitrile as the raw material synthesized 3 subphthalocyanines X-BsubPc(X = Br,Cl,F),their production rates were respectively 28.37 %,38.97 % and 10.43 %;finally all these compounds were characterized by FT-IR?1H NMR?13C NMR?and MS.The ultraviolet-visible(UV)absorption spectrum,fluorescence spectrum(FL)were measured to study their optical properties;the electrochemical properties were studied by testing cycle volt-ampere curve(CV);furthermore,the thermal properties was studied by thermogravimetric curve(TGA).The photophysicall performance test results show that: in different solvent,the maximal absorption peaks of the 3 metal hexadecafluorophthalocyanines are in the range of 665 ~ 720 nm;dodecafluorosubphthalocyanines are in the range of 570 ~ 580 nm;subphthalocyanines are in the range of 560 ~ 570 nm.The electrochemical testing results show that: the LUMO energy value of metal hexadecafluorophthalocyanines is in the range of-4.57 ~-4.50 eV;dodecafluorosubphthalocyanines is in the range of-4.08 ~-4.05 eV;subphthalocyanines is in the range of-4.03 ~-4.00 eV.The test result of thermal stability show that all these compounds have the good thermal stability as: the decomposition temperature(Td)of these 3 metal hexadecafluorophthalocyanines all over 380 ?;dodecafluorosubphthalocyanines all over 360 ?;subphthalocyanines are all over 280 ?.In addition,selecting zinc hexadecafluorophthalocyanine as the active layer material applied in organic field-effect device and showed the n-channel characteristics.Its mobility is 1.3 × 10-2 cm2 / V s.