Conjugated semiconducting organic materials for electronic applications

Since conjugated polymers, i.e. polymers with spatially extended pi-bonding system have offered unique physical properties, unobtainable for conventional polymers, significant research efforts directed to better understanding of their chemistry, physics and engineering have been undertaken in the past two and half decades. In this thesis we discuss the synthesis, characterisation and investigation of conjugated semiconducting organic materials for electronic applications. Owing to the versatile properties of metal-organic hybrid materials, there is significant promise that these materials can find use in optical or electronic devices in the future. In addressing this issue, the synthesis of bisthiazol-2-yl-amine (BTA) based polymers is attempted and their metallation is investigated. The focus of this work has been to examine whether the introduction of coordinating metal ions onto the polymer backbone can enhance the conductivity of the material. These studies can provide a basis for understanding the photophysical properties of metal-organic polymers based on BTA. In their neutral (undoped) form conjugated polymers are semiconductors and can be used as active components of plastics electronics such as polymer light-emitting diodes, polymer lasers, photovoltaic cells, field-effect transistors, etc. Toward this goal, it is an objective of the study to synthesize and characterize new classes of luminescent polymeric materials based on anthracene and phenanthrene moieties. A series of materials based on polyphenylenes and poly(phenyleneethynylene)s with 9,10-anthrylene subunits are not only presented but the synthesis and characterization of step-ladder and ladder poly(p-phenylene-alt-anthrylene)s containing 9,10-anthrylene building groups within the main chain are also explored. In a separate work, a series of soluble poly-2,7- and 3,6-phenanthrylenes are synthesized. This can enable us to do a systematic investigation into the optical and electronic properties of PPP-like versus PPV-like. Besides, the self-organization of 3,6-linked macrocyclic triphenanthrylene has been investigated by 2D wide-angle X-ray scattering experiments performed on extruded filaments in solution and in the bulk. Additionally, from the concept that donor-acceptor materials can induce efficient electron transfer, the covalent incorporation of perylene tetracarboxydiimide (PDI) into one block of a poly(2,7-carbazole) (PCz)-based diblock copolymer and 2,5-pyrrole based on push-pull type material are achieved respectively.

Optical transitions and type-II band lineup of MBE-grown GaNAs/GaAs single-quantum-well structures

We have investigated transitions above and below band edge of GaNAs/GaAs and InGaNAs/GaAs single quantum wells (QWs) by photoluminescence (PL) as well as by absorption spectra via photovoltaic effects. The interband PL peak is observed to be dominant under high excitation intensity and at low temperature. The broad luminescence band below band edge due to the nitrogen-related potential fluctuations can be effectively suppressed by increasing indium incorporation into InGaNAs. In contrast to InGaNAs/GaAs QWs, the measured interband transition energy of GaNAs/GaAs QWs can be well fitted to the theoretical calculations if a type-II band lineup is assumed. (C) 2001 Elsevier Science B.V. All rights reserved.

Optical transitions and type-II band lineup of MBE-grown GaNAs/GaAs single-quantum-well structures

We have investigated transitions above and below band edge of GaNAs/GaAs and InGaNAs/GaAs single quantum wells (QWs) by photoluminescence (PL) as well as by absorption spectra via photovoltaic effects. The interband PL peak is observed to be dominant under high excitation intensity and at low temperature. The broad luminescence band below band edge due to the nitrogen-related potential fluctuations can be effectively suppressed by increasing indium incorporation into InGaNAs. In contrast to InGaNAs/GaAs QWs, the measured interband transition energy of GaNAs/GaAs QWs can be well fitted to the theoretical calculations if a type-II band lineup is assumed. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis of GaN nanowires and nano-pyramids in a two-hot-boat chemical vapor deposition system via an in-doping technique

A two-hot-boat chemical vapor deposition system was modified from a thermal evaporation equipment. This system has the advantage of high vacuum, rapid heating rate and temperature separately controlled boats for the source and samples. These are in favor of synthesizing compound semiconducting nano-materials. By the system, we have synthesized high-quality wurtzite single crystal GaN nanowires and nanotip triangle pyramids via an in-situ doping indium surfactant technique on Si and 3C-SiC epilayer/Si substrates. The products were analyzed by x-ray diffraction, field emission scanning electron microscopy, highresolution transmission electron microscopy, energy- dispersive x-ray spectroscopy, and photoluminescence measurements. The GaN nanotip triangle pyramids, synthesized with this novel method, have potential application in electronic/ photonic devices for field-emission and laser.

In0.25Ga0.75As growth on low-temperature thin buffer layers formed on GaAs (001) substrate

High-quality In0.25Ga0.75As films were grown on low-temperature (LT) ultra-thin GaAs buffer layers formed on GaAs (0 0 1) substrate by molecular beam epitaxy. The epilayers were studied by atomic force microscopy (AFM), photo luminescence (PL) and double crystal X-ray diffraction (DCXRD), All the measurements indicated that LT thin buffer layer technique is a simple but powerful growth technique for heteroepitaxy. (C) 2002 Elsevier Science B.V. All rights reserved.

Shallow donor defect formation and its influence on semi-insulating indium phosphide after high temperature annealing with long duration

Fe-doped semi-insulating (SI) InP has become semi-conducting (SC) material completely after annealing at 900 V for 10 hours. Defects in the SC and SI InP materials have been studied by deep level transient spectroscopy (DLTS) and thermally stimulated current spectroscopy (TSC) respectively. The DLTS only detected Fe acceptor related deep level defect with significant concentration, suggesting the formation of a high concentration of shallow donor in the SC-InP TSC results confirmed the nonexistence of deep level defects in the annealed SI-InP. The results demonstrate a significant influence of the thermally induced defects on the electrical properties of SI-InP. The formation mechanism and the nature of the shallow donor defect have been discussed based on the results.

Molecular beam epitaxial growth of GaN on 3c-SiC/Si(111) substrates using a thick AIN buffer layer

Hexagonal GaN films (similar to 3 mu m) were grown on 3c-SiC/Si(111) and carbonized Si(111) substrates using a thick AlN buffer Cracks are observed on the surface of the GaN film grown on the carbonized Si(111), while no cracks are visible on the 3c-SiC/Si(111). XRD exhibits polycrystalline nature of the GaN film grown on the carbonized Si(111) due to poorer crystalline quality of this substrate. Raman spectra reveal that all GaN layers are under tensile stress, and the GaN layer grown on 3c-SiC/Si(111) shows a very low stress value of sigma(xx) = 0.65 Gpa. In low-temperature Photoluminescence spectra the remarkable donor-acceptor-pair recombination and yellow band can be attributed to the incorporation of Si impurities from the decomposition of SiC.

Growth and characterization of 4H-SiC by horizontal hot-wall CVD

4H-SiC layers have been homoepitaxially grown at 1500 degrees C with the use of a horizontal hot-wall chemical vapor deposition (CVD) system, which was built in the author's group. The typical growth rate was 2 mu m/h at a pressure of 40 Torr. The background donor concentration has been reduced to 2.3 x 10(15) cm(-3) during a prolonged growth run. It confirmed the idea that the high background concentration of thin films was caused by the impurities inside the susceptor and thermal insulator The FWHM of x-ray co-rocking curves show 9 similar to 15 aresecs in five different areas of a 32-mu m-thick 4H-SiC epilayer The free exciton peaks dominated in the near-band-edge low-temperature photoluminescence spectrum (LTPL), indicating high crystal quality.

Controlled growth of III-V compound semiconductor nano-structures and their application in quantum-devices

Various techniques on the growth of self-assembled compound semiconductor nano-structures (quantum dots, QDs) have been tried to enhance the controlling on size, density, emitting wavelength, uniformity in size and ordering in location of the QDs. Optimized growth conditions have been used in the application of the QD materials in opto-electronic devices. High-power long-lifetime quantum-dot laser-diodes (QD-LDs) emitting near 1 mu m, QD-LDs emitting in red-light range, 1.3 mu m QD-LDs on GaAs substrate and quantum-dot super-luminescent diodes (QD-SLDs) have successfully been achieved.

Molecular-beam epitaxial growth of position controlled InAs islands on cleaved edge of InGaAs/GaAs superlattice

A promising approach for positioning of InAs islands on (110)GaAs is demonstrated. By combining self-assembly of quantum dots with solid source molecular beam epitaxy (MBE) on cleaved edge of InGaAs/GaAs superlattice (SL), linear alignment of InAs islands on the InGaAs strain layers have been fabricated The cleaved edge of InGaAs/GaAs SL acts as strain nanopattern for InAs selective growth. Indium atoms incident on the surface will preferentially migrate to InGaAs regions where favorable bonding sites are available. The strain nanopattern's effect is studied by the different indium fraction and thickness of InxGa1-xAs/GaAs SL. The ordering of the InAs islands is found to depend on the properties of the underlying InGaAs strain layers.

Effect of noncoherent islands on the optical properties of the 1.3 mu m InAs/GaAs quantum dots during rapid thermal annealing

The effect of thermal annealing of InAs/GaAs quantum dots (QDs) with emission wavelength at 1.3 mu m have been investigated by photoluminescence (PL) and transmission electron microscopy (TEM measurements. There is a dramatic change in the A spectra when the annealing temperature is raised up to 800 degrees C: an accelerated blushifit of the main emission peak of QDs together with an inhomogeneous broadening of the linewidth. The TEM images shows that the lateral size of normal QDs decreases as the annealing temperature is increased, while the noncoherent islands increase their size and densit. A small fraction of the relative large QDs contain dislocations when the annealing temperature increases up to 800 degrees C. The latter leads to the strong decrease of the PL intensity.

Micro-fabricated Al0.3Ga0.7As pyramids for potential SPM applications

A novel technique of manufacturing Al0.3Ga0.7As pyramids by liquid phase epitaxy (LPE) for scanning probe microscopy (SPM) sensors is reported Four meticulously designed conditions-partial oxidation, deficient solute, air quenching and germanium doping result in defect-free homogeneous nucleation and subsequent pyramid formation. Micrometer-sized frustums and pyramids are detected by scanning electron microscopy (SEM). The sharp end of the microtip has a radius of curvature smaller than 50 nm. It is believed that such accomplishments would contribute not only to crystal growth theory, but also to miniature fabrication technology.

Raman scattering study on diluted magnetic semiconductor Ga1-xMnxAs prepared by Mn-ion implantation

Raman scattering measurements have been performed in diluted magnetic semiconductor Ga1-xMnxAs prepared by Mn-ion implantation, deposition, and post-annealing technique. It is found that the Raman spectrum measured from the implanted surface of the sample shows some new weak modes in addition to the GaAs-like modes which are observed from the unimplanted surface. The new vibrational modes observed are assigned to MnAs-like modes. The coupled LO-phonon plasmon mode, and Mn and As related vibrational modes caused by Mn-ion implantation, deposition, and post-annealing are also observed. Furthermore, the GaAs-like modes are found to be shifted by approximately 4 cm(-1) in the lower frequency side, compared with those observed from the unimplanted surface.

Edge dislocation of b=[001]/2 in the InAs nanostructure on InP(001)

The self-organized InAs/In0.52Al0.48As nanostructure were grown on InP (001) using molecular beam epitaxy (MBE). The nanostructure has been studied using transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). The edge dislocations with the Burgers vector b = ([001]/2) and extending along the [$(110) over bar $] direction are observed. The results show that in the region near an edge dislocation, no InAs wires were formed, while in the regions free of dislocation, wire-like nanostructures were formed. The mechanisms for the formation of the [001]/2 edge dislocations were discussed.

Space-grown SI-GaAs and its application

A semi-insulating GaAs single crystal ingot was grown in a recoverable satellite, within a specially designed pyrolytic boron nitride crucible, in a power-travelling furnace under microgravity. The crystal was characterized systematically and was used in fabricating low noise field effect transistors and analogue switch integrated circuits by the direct ion-implantation technique. All key electrical properties of these transistors and integrated circuits have surpassed those made from conventional earth-grown gallium arsenide. This result shows that device-grade space-grown semiconducting single. crystal has surpassed the best. terrestrial counterparts. Studies on the correlation between SI-GaAs wafers and the electronic devices and integrated circuits indicate that the characteristics of a compound semiconductor single crystal depends fundamentally on its stoichiometry.