Circuit Simulation for the Dielectric Responses of the Composites of Copper Phthalocyanine Oligomers and Sulfonated Polyurethanes by Separating the Structural ElementsJUAN ZHANG,1DAN ZHU,1,2MASARU MATSUO 11Graduate School of Humanities and Sciences,Faculty of Human Life and Environment,Nara Women’s University,Nara 630-8263,Japan2Jiangsu Key Laboratory of Biofunctional Materials,College of Chemistry and Environment Science,Nanjing Normal University,Nanjing 210097,People’s Republic of ChinaReceived 14January 2009;revised 3March 2009;accepted 29March 2009DOI:10.1002/polb.21720Published online in Wiley InterScience ().ABSTRACT:The copper phthalocyanine (CuPc)oligomer with high dielectric constantwas synthesized by the solution method.The FT-IR and X-ray diffraction results revealed its chemical structure.The high dielectric constant of CuPc was proved to result from the free movement of charge carriers along the conjugated orbitals.The com-posites of CuPc and sulfonated polyurethane (PUI)were prepared and the contents of CuPc in the composites were varied from 10to 50wt %.The dielectric performance was greatly enhanced for the composite compared with that of average polymers.Different from the behaviors appeared in a common composite with conductive fillers,there is no percolation phenomenon observed in the CuPc/PUI composite,and the dielectric con-stants of CuPc/PUI composites decreased with the increase in the CuPc content,which is assumed to due to the strong electrostatic interactions between CuPc and PUI.Con-sidering the many-body interactions within the bulk sample and the contact effect between the bulk sample and the metallic electrode,an equivalent circuit was estab-lished to simulate the dielectric behaviors of the composites and computational curve fit-ting was done.The results were in good agreement,indicating that the dielectric responses of the composites come from both the extrinsic and the intrinsic contributions.The extrinsic was associated with the Maxwell-Wagner relaxation at the interface between the electrode and the bulk sample,and the intrinsic was associated with the huge dipoles provided by the mobile charges within the CuPc grains and the interaction among them in the bulk composites.A circuit model concerning the universal dielectric response was proposed in describing the intrinsic contribution,which quantitatively verified the strong interaction among the dipoles with the relaxation time,representingthe aggregated structure of CuPc when its content was high in the composites.VC 2009Wiley Periodicals,Inc.J Polym Sci Part B:Polym Phys 47:1146–1155,2009Keywords:composites;dielectric properties;equivalent circuit;phthalocyanines;simulationsINTRODUCTIONElectroactive polymers (EAPs)are of great inter-est for a wide range of exciting applications,suchas electromechanical and dielectric devices,Journal of Polymer Science:Part B:Polymer Physics,Vol.47,1146–1155(2009)VC 2009Wiley Periodicals,Inc.Correspondence to:D.Zhu (E-mail:zhudan1013@)or M.Matsuo (E-mail:m-matsuo@cc.nara-wu.ac.jp)1146because of their many attractive features,such as light weight,high mechanicalflexibility,and con-formability.1–4To satisfy the requirement for a high-performance electro-mechanical material,a high-dielectric constant is demanded to generate a high elastic energy under low appliedfield.5,6There are two major categories of EAPs depending on their mode of activation mecha-nism,that is,electronic and ionic categories,met-allophthalocyanines are assigned to the latter. Electricfield or Coulomb forces generally drive electronic EAPs,whereas the primary driver for ionic EAPs is the mobility or diffusion of ions. Since the discovery of their semiconductivity in 1948,7metallophthalocyanines have become one of the most interesting classes of organic semicon-ductors,because they are planar,highly aromatic, symmetrical,and thermally stable compounds.8 Metallophthalocyanine polymers can be synthe-sized through metal–metal bonding or covalent bonding between the phthalocyanine rings and the extent of conjugation and delocalization can be enhanced by polymerization,leading to their unusual electrical properties,which have attracted considerable attention in recent years.9 Copper-phthalocyanine(CuPc),which has a high dielectric constant at room temperature due to the nomadic polarization mechanism(delocalized electrons lead to the space charge phenomenon),10 is a promising material for dielectric application. Nevertheless,they are brittle and difficult to pro-cess,11leading to an appeal to an appropriate polymer matrix which is easy to obtain and be processed to prepare a composite with high dielec-tric constant.In2000,an organic polymeric composite based on CuPc oligomers and poly(vinylideneflu-oride-trifluoroethylene)[P(VDF-TrFE)]copolymer, which obtained huge dielectric constant,was found by H.Xu et al.12Whereas,in their research, the CuPc content has reached as high as55%for a composite with satisfactory dielectric properties. Hence,we dedicate tofind a better polymer ma-trix to fabricate a composite with high dielectric constant and low dielectric percolation threshold. The excellent dispersive condition of the CuPc is desired,and the ionized polyurethane(PUI), which is a material with polar group and possibly obtaining dipolar interactions and good miscibility with CuPc,provides the idea on solving this prob-lem.PUI molecules obtain high polarity and intrinsic dielectric constant than other polymers, which may be expected that the CuPc with car-boxylic acid functional groups will be easier and more complete to disperse in a matrix of PUI, obtaining a satisfactory polymer composite in physical properties.Therefore,the polymer com-posites of CuPc and PUI have been prepared and their dielectric properties have been characterized and analyzed from the view of micro-structures.The investigation on the dielectric properties provides a potential tool to illuminate the rela-tionship between the micro-structure and the macroscopic physical properties in a heteroge-neous system.The particular chemical structures of variousfillers can provide their different in-trinsic dielectric constant and affect their disper-sion in a polymer matrix,resulting in the differ-ent dielectric behaviors for the composites based on the same matrix and the differentfillers.Fur-thermore,the dielectric behaviors are strongly affected by the charge distribution and by the sta-tistical thermal motions of its polar groups.Espe-cially the study of relaxation process constitutes a powerful approach for obtaining information about the nature and types of molecular motions and the dispersion mode offillers that are affected by chemical compositions,molecular structure, morphology,etc.13In addition,the establishment of equivalent circuit,as well as the application of mathematical simulation,will reasonably and precisely elucidate the mechanism and origin of the dielectric behaviors of the heterogeneous composites.In our experiment,the CuPc oligomers were synthesized by the solution method and charac-terized by structural analysis to verify their highly planar-conjugated structure,which can provide a large delocalized orbital for electron delocalization,thus leading to a huge intrinsic dielectric constant.CuPc is selected as reinforce-mentfillers to fabricate its composites with PUI matrix.Though they obtain the polarization mechanism as other conjugated polymers,such as polyaniline and polyacene quinone radical poly-mers,they show the unique dielectric reinforce-ment effect and the mechanism on their compo-sites.The interfacial status in the CuPc/PUI com-posites is investigated,and the relationship between the microscopic hetero-structures and the physical properties is studied.An equivalent circuit has been established to explore the origin and the character of the dielectric behaviors of the composites.Thefitting results,which are in good agreement with the experimental data, reveal that there are two contributions to the dielectric properties,the intrinsic contribution based on the bulk sample and the extrinsicDIELECTRIC BEHAVIORS OF COPPER PHTHALOCYANINE OLIGOMERS1147Journal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polbcontribution from the contact effect between thesample and the electrode.EXPERIMENTALMaterialsPyromellitic dianhydride(PMA)was purchasedfrom Shanghai Chemical Reagent Co.,Pellethane50,a condensate of methylene diphenyl-diisocya-nate(MDI),poly(tetramethyl glycol)(PTMO,MW ¼1000),and1,4-butanediol(BD)with a molar ra-tio3.3/2.3/1.0,was purchased from Dow Chemi-cals.Sodium hydride and1,3-propane sultone(97%)were from Aldrich Chemical Company,theother reagents were commercial chemicals. SynthesisSynthesis of Copper-Phthalocyanine OligomerThe CuPc oligomer was synthesized by the solu-tion method.11Copper sulfate pentahydrate,PMA,urea,ammonium chloride and ammoniummolybdate calculated according to an appropriatemolar ratio were ground together and then placedin a three-neckedflask equipped with thermome-ter,condenser,and mechanical stirrer.Nitroben-zene was used as solvent,and the temperature of reaction solution was increased slowly from the room temperature and then maintained at180–185 C for12h.The as-synthesized solid materi-als wasfinely ground and washed with methanol to remove nitrobenzene completely.The powder was boiled in2M hydrochloric acid saturated with sodium chloride for several minutes andfiltered after cooling to room temperature.The product was neutralized by2M sodium hydroxide solution containing sodium chloride at90 C until the am-monia was completely gotten rid of.The precipi-tate was solved in2M hydrochloric acid and then centrifugated.After centrifugation,the product was dried at room temperature under vacuum. The synthesis route of CuPc oligomer is displayed in Scheme1.Synthesis of PUIThe synthesis route of PUI displays in Scheme2. Reaction was performed in a three-neckedflask equipped with condenser,drying tube,thermome-ter,magnetic stirrer,and nitrogen inlet.Theflask wasflamed outside while swept by nitrogenforScheme2.The synthesis route of the sulfonated PUI.1148ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polbanhydrous circumstance.Pellethane was dis-solved in anhydrous N,N-dimethyl-formamide (DMF),and then cooled to aboutÀ5 C with a salt-ice bath.Calculated amount of sodium hydride was added intoflask with vigorous stir-ring and reacted for1h until all of the sodium hydride had been consumed to obtain a greenish-yellow solution.Previously calculated propane sultone was added to the metallated polyurethane reaction mixture and continued to react at about 0 C for0.5h.The ice-salt bath was removed,and stirring was continued for another0.5h at room temperature,and then at50–60 C for another 1h.Followed by addition of toluene and removal of the excessive solvent,the reaction mixture was precipitated.Then the precipitates were washed by water and dried in vacuum for48h to obtain thefinal product.Preparation of CuPc/PUI Composite FilmsThe compositefilms of CuPc/PUI were prepared by solution casting.The solution of PUI in DMF was prepared,and the CuPc particles were dis-persed in the prepared PUI solution under ultra-sonic treating for2h.The compositefilms were obtained by a solution-casting method and dried in air at60 C for12h,followed by vacuum dry-ing at60 C for24h to completely evaporate the remnant solvent.The thicknesses of all thefilms were about100–200l m.CharacterizationAll samples were completely dried in a vacuum desiccant for24h at room temperature to get rid of the residual solvent before testing.The FT-IR spectrum was taken by the Fourier transform infrared spectrophotometer of Bruker Vector-22 FT-IR with the standard laser spectrum of 632.8nm.Samples were ground,mixed with po-tassium bromide,and compressed to pellets for testing.X-ray measurements were performed by a 12-kW rotating-anode X-ray generator(Shimadzu XD-3AX)with a point focusing,and the mono-chromatic Cu K a radiation(wavelength of0.1542 nm)was used.Samples tested were in powder form for CuPc,as well as in thefilm forms for PUI and the composites.Corrections of X-ray diffrac-tion intensity were made for air scattering,back-ground noise,polarization and absorption.The measurement for the content of the carbox-ylic radicals in CuPc was performed by the poten-tiometrictitration and back titration.The content of the copper in CuPc was measured by induc-tively coupled plasma atomic emission spectrome-try(ICP Jarrell-Ash J-A1100),the potassium salts solution of CuPc was prepared for testing.The dielectric spectra were recorded by the Im-pedance Analyzer(HP4194A/RT)from Agilent Co. Before the measurements,the samples were hot-pressed under80 C for10min,and then vacuum evaporated with Au electrode by an Ion Coater, Hitachi Eiko IB-3with the coating area of 4.9mm2.The measuring voltage was0.5V, and the frequency was in the range from100Hz to10MHz.RESULTS AND DISCUSSIONThe FT-IR spectrum of CuPc oligomer is shown in Figure1.The broad absorption band from3500to 3000cmÀ1is assigned to the O A H stretching vibration in carboxylic acid,then combining the strong C A O stretching vibration around 1710cmÀ1,the existence of carboxylic acid func-tional groups can be verified.A mild absorption band observed around920cmÀ1can be attributed to the metal-ligand vibration resulting from bond-ing between the copper atom and the nitrogen atoms in the four surrounding isoindole rings,14,15 which is the most important characteristic of met-allophthalocyanines.Another absorption band around810cmÀ1is also assigned to the metal-ligand vibration.16–18In addition,the absorption bands observed around1628,1580,1508,1456, and1096cmÀ1are assigned to phthalocyanine skeletal vibration,namely,the C A C or C A N stretching deformation in the large conjugated plane of CuPc.The absorption bands observed around1135and731cmÀ1correspond to the C A H in-plane bending deformation and the C A H out-of-plane bending deformation of the periph-eral benzene rings of CuPcmolecule, Figure1.The FT-IR spectrum of CuPc oligomer.DIELECTRIC BEHAVIORS OF COPPER PHTHALOCYANINE OLIGOMERS1149Journal of Polymer Science:Part B:Polymer PhysicsDOI10.1002/polbrespectively .19,20The results are coincident with the established values reported.21–24The content of carboxylic acid functional groups in CuPc obtained from the back titration is 24.48wt %,a little lower than the value of 25.40wt %from the theoretical calculation in which CuPc oligomer is regarded as a homopoly-mer of tetramers.Actually ,it is impossible to obtain the tetramers only from the synthetic pro-cess,and the dimers,trimers even multimers are also possibly synthesized at the same ly,the CuPc tetramer oligomer obtained is mixed with a small amount of various unimers of other degree of polymerization,resulting in the deviation from the theoretical value.Although the experimental result is very close to the theoretical value,it indicates that the CuPc oligomers obtained are mostly the tetramers.Moreover,the condensation reaction between few carboxylic acid groups possibly occurs,leading to a decrease of the content of the carboxylic acid functional groups.In contrast,the result of element analysis dem-onstrates that the copper content in CuPc oligomer is 6.08%,which is 81.94%of the theoreti-cal value of 7.42%.The deviation of the copper content from the theoretical value may be due to the partial demetallization of the copper from the phthalocyanine rings during the synthetic plex formation takes place between cop-per and chloride ions during HCl-washing and the copper salt is separated out leaving behind the metal-free phthalocyanine macrocyclic struc-ture,10,14resulting in the decrease of the copper content in CuPc.The dielectric constant of CuPcoligomer is significantly affected by its copper con-tent,the dielectric constant will decrease dramati-cally after treatment by HCl.10Figure 2shows the wide-angle X-ray diffraction intensity curves taken for CuPc oligomer.Based on the Bragg formula,for CuPc,the interplanar spacings corresponding to the diffraction peaks situated around 2h ¼9.1,10.3,26.9,and 28.3oare given as 9.72,8.59,3.31,and 3.15A˚,respec-tively ,which verify the crystalline structures of CuPc.25–28The strong reflection from the crystalplane with lattice space of 3.31A˚in distance,is a typical peak observed from the planar structures of carbon or graphite,29,30implying that CuPc obtains the highly conjugated structure based on the stacking of the graphite-like planes.In addi-tion,the strong diffraction peak around 28.3 is assigned to the second-order reflection (004),due to the existence of copper atom which can make the extra contribution to the scattering.31The results from X-ray indicate that Cu atoms and the four surrounding isoindole nitrogen atoms must all lie strictly in one plane,and Cu atoms are bound by covalent bond to the four isoindole nitro-gen atoms.31The whole CuPc molecule obtains the extended conjugated structure in a plane,which can provide huge p -associated orbital for electron delocalization.The existence of copper allows a further increase of the delocalization due to the bridge bonding.Thus a large polarization occurs,providing a high dielectric constant to the intrinsic CuPc.The frequency dependence of bulk dielectric constant and loss tangent of CuPc oligomers at room temperature are shown in Figure 3.The dielectric constant of CuPc can reach 7Â105at the frequency of 100Hz,and gradually dropstoFigure 3.The frequency dependence of the dielec-tric behavior of CuPc oligomer.1150ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI 10.1002/polb200at107Hz.The strong dielectric dispersion at low frequency is characteristic for a charge carrier system.The high dielectric constant in CuPc is due to a kind of colossal polarization,termed as ‘‘nomadic polarization’’by Pohl.32–34In a molecu-lar view,there are large amounts of charge car-riers in CuPc created intrinsically by naturally dissociation of the conjugated polymers.These mobile charges would move freely along extended regions provided by the associated p-orbital with near-zero resistance,and are ultimately limited by a boundary.Those conjugated planar or stacked‘‘huge molecular orbital(MO)poly-mers.’’32will form a collection of highly polarized polarons,35thereby exhibit high bulk permittivity under the external electricfield.In CuPc or its composite in this article,the most contributions to the dielectric constant at the low frequencies are those huge polarons,that is,the grains of CuPc.For CuPc,there are two reasons to cause the dielectric losses at the frequencies in our mea-surement range.One is the conduction loss from the movement of charges along the huge delocal-ized conjugated orbitals,which consumes the elec-trical energy.The other is the relaxation loss pro-duced under the process of polarization because of the hindrance to the movements of the polarons, including atoms,groups,and the whole molecules, resulting in the energy consumption in overcom-ing the internal viscous resistance during the ori-entation of the polarons.Both the dielectric constant and loss tangent of CuPc decrease with the increasing frequency, which is attributed to the fact that the polarons with large dipole moments provides an increase in the dielectric constant for CuPc.Meanwhile,it also provides an increase in the dielectric loss tan-gent due to the enhanced electronic conductance and the enhanced hindrance from the interaction between the polarons.Because both the nomadic polarization and the displacement of the electrons are proportional to the size of the polarons or the delocalized regions,the dielectric loss tangent increases with the increase of the dielectric con-stant,as shown in Figure3.On the basis of the above structural discussion, CuPc oligomers have high bulk dielectric constant and their polarization mechanism is the same as that of other conjugated organic semiconductors. Hence,to explore the dielectric reinforcement effect and mechanism of the PUI composites with CuPc,we fabricated the CuPc/PUI composites in which CuPc was used asfillers and thefiller con-tents varying from10to50%.The change of the dielectric constants of CuPc/PUI composites ver-sus the CuPc content is shown in Figure4.As observed from Figure4,the dielectric con-stants of CuPc/PUI composites decrease with increasing CuPc contents.It lies in the fact that CuPc obtains a lot of carboxylic groups,which can form a strong electrostatic force with the ionic groups in PUI,thus improving the dispersion of CuPc in PUI,so that the dielectric constant of the composite is high even in low content of CuPc. The lower the CuPc content is,the better disper-sion of CuPc in PUI is.With CuPc content increasing,the CuPc particles get close to each other and aggregate,which result in the enhance-ment of the interaction among the charges in the neighboring grains of CuPc.It is the long-range free moving of those charges that provide the huge permittivity of the bulk composite,so with the aggregation of CuPc and with the retarding of the charge mobility,the dielectric constants decrease.The aggregation of CuPc can be observed from X-ray diffraction spectra as shown in Figure5.PUI displays an amorphous phase and there is no detectable crystalline phase in PUI matrix due to the mergence of the hard segment and soft segment of polyurethane after ionization.While for CuPc/PUI composite with 25wt%CuPc content,there exists a diffraction peak around2h%27 which is due to CuPc crys-tal,indicating that CuPc has formed obvious aggregates when its content is25wt%.Figure6shows the frequency dependence of the dielectric behaviors for CuPc/PUI composites with various weight ratios of CuPc.A step-like increase in the dielectric constant towardlowerfrequencies is accompanied by a corresponding loss peak.Such Debye-like dipolar relaxation is mainly accounted for a large dielectric response at low frequency and the behavior can be explained by the contact effect.36It is of common sense that if the electron work function in a metal is different with that in a semiconductor,a thin layer which is made of mo-bile electron carriers will appear in the semicon-ductor close to the junction.This depletion layer acts as a high capacitance in parallel with a large resistor,connected in series to the bulk sample.For CuPc/PUI composite with 10wt %CuPc con-tent,the composites are semiconductive and the depletion regions may be formed at the interface between the composites and the metallic electro-des,leading to Maxwell-Wagner-type relaxations and giant dielectric constant at low frequency.In addition,as discussed above,CuPc particles get close to each other and aggregate with increasing the CuPc content,leading to the decrease of the concentration of space charges on the interface between the bulk sample and the electrodes.Meanwhile,the aggregation of CuPc particles makes it difficult for the huge dipoles formed or orientated to follow the change of the applied field,because of the enhanced hindrance to the orientation of the dipoles from the neighboring circumstance,that is,the interaction among the charges within the neighboring grains of CuPc.Therefore,with the CuPc content increasing,the relaxation peaks move towards low frequencies and the intensities of relaxation decrease.Besides the extrinsic contribution from the con-tact effect,the intrinsic dielectric response attrib-uted to the bulk sample also contributes to the total dielectric behaviors.Considering the many-body interactions within the huge dipoles of the CuPc grains,the intrinsic dielectric response is addressed by the sum of DC conductivity ,fre-quency dependent AC conductivity and the infi-nite dielectric constant e 1at high frequency.According to the theory of the universal dielectric response by Jonscher,37the intrinsic contribution of the bulk sample can be described by:e 0intrinsic ¼tan n p 2 r0e 0x n À1þe 1(1)where x ¼2p f is angular frequency,r 0x n is the universal dielectric response (UDR)used for fre-quency dependence AC conductivity ,e 0is vaccum permittivity,and n is an exponential factor with the value between 0and 1.Considering the extrinsic contribution from the contact region,which is Debye-likerelaxation,Figure 6.The frequency dependence of (a)the dielectric constant and (b)loss tangent for CuPc/PUI composites with different weightratios.Figure 5.The X-ray diffraction spectra of PUI and CuPc/PUI composite with 25wt %CuPc content.1152ZHANG,ZHU,AND MATSUOJournal of Polymer Science:Part B:Polymer PhysicsDOI 10.1002/polbthe totally dielectric response can be exhibited as follows 36,38:e 0¼tan n p 2 r 0e 0x n À1þe 1þe c Àe 11þx 2s 2(2)The first and second terms on the right hand sideof the equation represent the response of the bulk sample at low and high frequency,and the last term represents the contribution of contact region.e c is the dielectric constant of contact region and s is the relaxation time which is single without distribution.The equivalent circuit and the fitting results are shown in Figure 7,the solid curve well fits the experiment data by eq 2and the dot line demon-strates the intrinsic response of the bulk sample.The values of the corresponding parameters obtained from the fit are listed in Table 1.The relax-ation time s is a parameter describing how fast a micro-system will get to new equilibrium with the change of the external circumstance.In most occa-sions,s represents the extent that the dipole is impeded in the orientation,or the extent that the charges are constrained in movement,that is,the interaction of nearby circumstance to the dipole.With increasing the CuPc content,the aggregation of CuPc makes the grains get close to each other,it makes the formation of the huge dipole more and more difficult in keeping up with the change of the applied field as for the enhanced interactions from the nearby charges in the neighboring dipoles,lead-ing to the increase in the relaxationtime.CONCLUSIONSThe CuPc oligomer with high bulk dielectric con-stant was synthesized by the solution method. The FT-IR and X-ray diffraction spectra were measured to characterize the chemical structure of CuPc,and it demonstrated that the origin of the high dielectric constant as well as its polariza-tion mechanism was the free movement of charge carriers along the conjugated orbitals.The CuPc/ PUI composites were prepared with CuPc con-tents varied from10to50%,demonstrating a characteristic reinforcement on the dielectric properties of the polymer.Different from the obvious percolation behavior observed for the composites of other condcutivefillers,the dielec-tric constants of CuPc/PUI composites decreased with the increase of the CuPc content,due to the fact that the strong electrostatic interactions between the carboxylic groups in CuPc and the ionic groups in PUI improves the dispersion of CuPc in the low content of CuPc,whereas the aggregation of CuPc at high content results in the decrease of the dielectric constant.Considering the many-body interactions within the bulk sample,as well as the contact effect between the bulk sample and the metallic elec-trode,an equivalent circuit was established to simulate the dielectric behaviors of the compo-sites.Thefitting results were in good agreement with the experimental data and indicated that the dielectric responses of the composites did come from two contributions.One was the extrinsic associated with the Maxwell-Wagner-type relaxa-tion at the interface between the electrode and the bulk sample,and the other,the intrinsic one was from the highly polarized CuPc grains that acted as huge dipoles in the composite.In describ-ing the intrinsic contribution,we used a model containing a universal dielectric response,repre-senting the unique aggregated structure of CuPc in the composites.It was verified by the relaxa-tion time that the interactions among CuPc dipoles increase with the increasing contents of CuPc.REFERENCES AND NOTES1.Zhang,Q.M.;Li,H.F.;Poh,M.;Xia,F.;Cheng,Z.Y.;Xu,H.S.;Huang, C.Nature2002,419, 284–287.2.Bar-Cohen,Y.J Spacer Rockets2002,39,822–827.3.Herbert,J.M.Ferroelectric Transducers and Sen-sors;Gordon and Breach Science Publishers:New York,1982.4.Dias,C.J.;Das-Gupta,D.K.IEEE Trans DielectrElectr Insul1996,5,706–734.5.Zhang,Q.M.;Bharti,V.;Zhao,X.Science1998,280,2101–2104.6.Bai,Y.;Cheng,Z.Y.;Bharti,V.;Xu,H.;Zhang,Q.M.Appl Phys Lett2000,76,3804–3806.7.Eley,D.D.Nature1948,162,8198.Moser,F.A.;Thomas,A.L.Phthalocyanine Com-pounds;Reinhold Publishing Corp.:New York, 1963.9.Meier,H.;Albrecht,W.;Zimmerhackl, E.PolymBull1985,13,43–50.10.Nalwa,H.S.;Dalton,L.R.;Vasudevan,P.EurPolym J1985,21,943–947.11.Achar, B.N.;Fohlem,G.M.;Parker,J. 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