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Aniline Black, a polymer containing p-benzoquinodiimine groups, was synthesized chemically or electrochemically by the oxidation of aniline. The polymer salts showed the conductivity of 10⁻¹-10⁻³ ohm⁻¹cm⁻¹. Polymers containing anthroquinodiimine units were also prepared by polycondensations. The syntheses of model compounds containing p-benzoquinodiimine were attempted. Multiazobisphenol monomers were synthesized. 4,4'-(3,3'-Dimethyl-4,4'-biphenylenebisazo) bisphenol 7, 4,4'-[azobis(p-phenyleneazo)] bisphenol 8, and 4,4'-(2-methoxy-1,4-phenylenebisazo) bisphenol 10 displayed liquid crystal (l.c.) properties, while model derivatives of 7, 8, and 4,4'-(4,4'-stilbenebisazo) bisphenol 9 did likewise. Monomers and derivatives of 4-[(4-hydroxyphenyl)azo]-1-naphthol 5, and 4,4'- [oxybis(p-phenyleneazo)] bisphenol 6 showed no l.c. behavior. New thermotropic polyesters based on these multiazobisphenols were synthesized. Sebacates of 5, 6, 7, 8, and 10 showed l.c. behavior, while polymers based on isophthalic or 5-t-butylisophthalic acid did not do so. Polyformals were also synthesized from these momoners, only that of 4 showed weak l.c. behavior. The correlation between the structure of these polymers and their tractabilities, electrical properties, liquid crystal behaviors was studied. Polymers and copolymers containing p-azoarylene and p-azoxyarylene groups were synthesized by oxidative coupling of various aromatic diamines. Films were cast directly from the reaction mixtures or from the polymer solution. The films were n-doped by sodium naphthalide or p-doped by iodine. They showed electrical conductivities of 10⁻⁴ to 10⁻⁵ ohm⁻¹cm⁻¹. AB monomers containing dipolar p-phenyleneazo groups were synthesized: 4-(4-hydroxy-2-methoxyphenylazo) benzoic acid 21, 4-[4-(4-hydroxy-2-methoxyphenylazo)-2-methoxyphenylazo] benzoic acid 22, and 4-(4-hydroxy-2-methoxyphenylazo)-3-nitrobenzoic acid 23. The monomers were polymerized by direct polycondensations. The polyester synthesized from 21 formed a red, transparent film. A polymethacrylate containing dipolar p-phenyleneazo groups in the side chains was also prepared by the free radical polymerization of 1- [3-methoxy-4-(p-nitrophenylazo)-phenoxy] hexyl methacrylate 28.

This thesis investigation concerns the optical and nonlinear electrical properties of n-InSb. Two specific areas have been studied. First is the magneto-optical study of magneto-donors, and second is the nonlinear dynamic study of nonlinear and chaotic oscillations in InSb. The magneto-optical study of InSb provides a physical picture of the magneto-donor levels, which has an important impact on the physical model of nonlinear and chaotic oscillations. Thus, the subjects discussed in this thesis connect the discipline of semiconductor physics with the field of nonlinear dynamics.

David I. Kosowsky. / "June 1, 1955." "This report is based on a thesis submitted to the Department of Electrical Engineering, M.I.T., ... ." / Bibliography: p. 59-60. / Army Signal Corps Contract DA36-039 sc-42607 Project 102B Dept. of the Army Project 3-99-10-022

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An expression for the dielectric susceptibility tensor of a cubic ionic crystal has been derived using the classical Liouville operator. The effect of cubic anharmonic forces is included as a perturbation on the harmonic crystal solution, and a series expansion for the dielectric susceptibility is developed. The most important terms in the series are identified and summed, yielding an expression for the complex susceptibility with an anharmonic contribution which is linearly dependent on temperature. A numerical example shows that both the real and imaginary parts of the susceptibility are continuous, finite functions of frequency.

The influence of uniaxial compression upon the Hall effect ad resistivity of cadmium-doped samples of InSb at 77 K, 64 K, and 12 K are reported. Unilaxial compressions as high as 6 kbar were applied to samples oriented in the {001} and {110} directions. The net hole concentration of the samples were about 5x10^13 cm^-3 at 77 K as determined from the Hall coefficient at 24 kilogauss. The net concentration of hole carriers decreases and then increases exponentially with stress at 77 k and 64 k, while at 12 k there is only a monotonic increase of carrier concentration with stress. Analysis of the hole concentration as a function of stress shows the presence of a deep acceptor level located about 90 meV above the valence band edge in additionb to the 10 meV vadmium acceptor level. The shallow acceptor level does not split with stress. The hole density data is represented very well by models which describe both the variation in the net density of states and motion of the acceptor levels as a function of stress.

The effects of optical heating via infrared free carrier absorption on the electron magneto-transport properties of n-InSb at helium temperatures have been studied for the first time. Oscillatory photoconductivity (OPC) type structure is seen in the photon energy dependence of the transport properties. A C0₂ laser (hω = 115 to 135 meV) was used as the optical source. Concentrations between 1 x 10¹⁵ cm⁻³ and 2 x 10¹⁶ cm⁻³ were studied. The conclusions of this study are that the energy relaxation of high energy photoexcited electrons, generated by free carrier absorption of C0₂ laser radiation in degenerate n-InSb at liquid helium temperatures, is by emission of a maximum number of optical phonons, and that this relaxation mechanism produces OPC type structure in the photon energy dependence of the electron temperature of the conduction band electron gas. This structure is seen, therefore, in the transport properties of the sample, including the Shubnikovde Haas effect, the effective absorption coefficient, and the photoconductivity (mobility) response (lower concentrations only). In addition, the highest concentration studied, nₑ = ~2 x 10¹⁶ cm⁻³, sets an experimental lower limit on the concentration at which electron-electron scattering will become the dominant energy relaxation mechanism for the photoexcited electrons, since OPC effects were present in this sample.

Indiana University-Purdue University Indianapolis (IUPUI) / Preparation and characterization of multiferroic materials in which ferroelectricity and ferromagnetism coexist would be a milestone for functionalized materials and devices. First, electric properties of polyvinylidene (PVDF) films fabricated using the Langmuir-Schaefer method have been studied. Films of different thickness were deposited on silicon substrates and analyzed using several techniques. X-ray diffraction (XRD) data showed that PVDF films crystallize at an annealing temperature above 130 °C. Polarization versus electric field (PE) ferroelectric measurements were done for samples prepared with electrodes. PE measurements show that the coercivity of the films increases as the maximum applied electric field increases. The coercivity dependence on the frequency of the applied electric field can be fitted as . The results also show that the coercivity decreases with increasing the thickness of PVDF film due to the pinning effect. Next, we have demonstrated that those PVDF properties can be controlled by applying an external magnetic field. Samples were created in a layered heterostructure, starting with a Fe thin film, PVDF above that, and followed by another thin film of Fe. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to study the interface between PVDF polymer films and ferromagnetic iron thin films. Conventional EXAFS was applied to identify the structure of a Fe film sandwiched between two PVDF layers. An electric signal was then applied to the polymer to study the effects polarizing the polymer has on the Fe atoms at the interface. This shows that the Fe atoms diffuse into the PVDF layer at the interface between the two layers. Polarizing the film causes further diffusion of Fe atoms into the polymer. We also found that as the applied magnetic field is changed, the switching of electric polarization for the PVDF displayed a dependence on the external magnetic field. We also noticed that both the coercivity and polarization for the PVDF polymer display hysteretic features as the applied magnetic field is changed. We also found that the thickness of both the iron layers and the PVDF layer has an effect on the magnetoelectric coupling in our samples. The same strain applied to a thicker PVDF layer becomes tougher to flip the polarization compared to a thinner PVDF layer. As the iron film thickness increases, the strain also increases, and the polarization of the PVDF polymer is more easily flipped. We also found that the magnetoelectric sensitivity increases as both the PVDF and iron layers increase in thickness. We have shown that it is possible to control the ferroelectric properties of a PVDF film by tuning the magnetic field in a heterostructure. Our experiments show a coupling between the electric polarization and applied magnetic field in multiferroic heterostructures much larger than any previously reported values. Previous reports have used inorganic materials for the ferroelectric layer. Organic polymers have an electric dipole originating at the molecular level due to atoms with different electronegativity that are free to rotate. To flip the polarization, the chains must rotate and the position of the atoms must change. This increases the force felt locally by those chains. Using this polymer, we are able to increase the magnetoelectric coupling.