Semiconductor devices based on III-V materials have been the focus of intense research due to their superior electron mobility and favorable energy direct bandgap which are applicable in infrared wavelength range optoelectronics and high speed electronic systems. The thesis presented here consists of two thrusts; the first focusing on infrared applications, and the second focusing on InP-based heterojunction bipolar transistors (HBTs). In the first thrust, we investigate type-II InAs/GaSb superlattice IR detector devices and the effect of substrate orientation on InSb and InAs nanostructure morphology. In the second thrust, we study InP-based high frequency HBTs. A low resistance InAs ohmic contact is demonstrated, and we presented along with a study of the crystalline qualities in GaAs0.5Sb0.5 films grown on tilted- axis InP substrates. Chapter 2 presents fabrication and characterization of two type-II superlattice structures with 15 monolayer (ML) InAs/12ML GaSb and 17ML InAs/7ML GaSb grown on GaSb (100) substrates by solid-source molecular beam epitaxy (MBE). The X-ray diffraction (XRD) measurements of both the 15ML InAs/12ML GaSb and 17MLInAs/7ML GaSb superlattices indicated excellent material and interface qualities. The cutoff wavelengths of 15ML InAs/12ML GaSb and 17ML InAs/7ML GaSb superlattices photodetectors were measured to be 6.6μm and 10.2μm, respectively. These different spectral ranges were achieved by growing alternating layers of varying thicknesses which allowed for bandgap engineering of the superlattices of InAs and GaSb. Lastly, a mid-IR type-II superlattice photodiode was demonstrated at 80K with a cutoff wavelength at 6.6µm. The device exhibited a near background limited performance (BLIP) detectivity at 80K and higher temperature operation up to 280K. In Chapter 3, we show that the (411) orientation, though not a naturally occurring surface, is a favorable orientation to develop a buffer layer into a super flat surface at a certain high growth temperature. The (411) surface is a combination of localized (311) and (511) surfaces but at a high growth temperature, adatoms can obtain enough energy to overcome the energy barrier between these localized (311) and (511) surfaces and form a uniform (411) surface with potential minima. This results in a super flat surface which is promising for high-density nanostructure growth. In this work, this is the first time that the highest InSb and InAs nanostructures density can be achieved on the (411) surface which is in comparison with the (100), (311), and (511) surfaces. Chapter 4 of this thesis addresses the use of an InAs layer as a low-resistance ohmic contact to InP-based heterostructure devices. Selective area crystal growth of InAs on a dielectric (Benzocyclobutene, BCB polymer) covered InP (100) substrate and direct growth of InAs on InP substrate were performed by MBE. Heavy doping of InAs using Te was carried out to determine the lowest sheet resistance. Based on scanning electron microscope (SEM) and XRD measurements, increasing substrate temperature from 210 ℃ to 350 ℃, led to an improvement in crystallinity from a polycrystalline layer to a single crystal layer with a corresponding improvement of surface morphology. Moreover, a narrow X-ray diffraction peak indicated full-relaxation of the inherent 3.3% lattice-mismatch in InAs/InP layers. Furthermore, around 290 ℃ a tradeoff was reached between crystallinity and optimized dopant incorporation of Te into InAs for the lowest sheet resistance. Lastly, Chapter 5 discusses the effect of substrate tilting on the material properties of MBE grown GaAsSb alloys closely lattice-matched to an InP substrate. InP(100) substrates tilted 0°off-(on-axis), 2°off-, 3°off-, and 4°off-axis were used for MBE growth; then the material qualities of GaAsSb epitaxial layers were compared using various techniques, including high resolution XRD, photoluminescence (PL) and transmission-line measurements (TLM). Substrate tilting improved the crystalline quality of the GaAsSb alloys, as shown by a narrower XRD linewidth and enhanced optical quality as evidenced by a strong PL peak. The results of TLM show that the lowest sheet resistance was achieved at a 2° off-axis tilt.

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Graphene has emerged as an appealing material for a variety of optoelectronic applications due to its unique electrical and optical characteristics. In this thesis, I will present recent advances in integrating graphene and graphene-boron nitride (BN) heterostructures with confined optical architectures, e.g. planar photonic crystal (PPC) nanocavities and silicon channel waveguides, to make this otherwise weakly absorbing material optically opaque. Based on these integrations, I will further demonstrate the resulting chip-integrated optoelectronic devices for optical interconnects. After transferring a layer of graphene onto PPC nanocavities, spectral selectivity at the resonance frequency and orders-of-magnitude enhancement of optical coupling with graphene have been observed in infrared spectrum. By applying electrostatic potential to graphene, electro-optic modulation of the cavity reflection is possible with contrast in excess of 10 dB. And furthermore, a novel and complex modulator device structure based on the cavity-coupled and BN-encapsulated dual-layer graphene capacitor is demonstrated to operate at a speed of 1.2 GHz. On the other hand, an enhanced broad-spectrum light-graphene interaction coupled with silicon channel waveguides is also demonstrated with ∼0.1 dB/μm transmission attenuation due to graphene absorption. A waveguide-integrated graphene photodetector is fabricated and shown 0.1 A/W photoresponsivity and 20 GHz operation speed. An improved version of a similar photodetector using graphene-BN heterostructure exhibits 0.36 A/W photoresponsivity and 42 GHz response speed. The integration of graphene and graphene-BN heterostructures with nanophotonic architectures promises a new generation of compact, energy-efficient, high-speed optoelectronic device concepts for on-chip optical communications that are not yet feasible or very difficult to realize using traditional bulk semiconductors.

published_or_final_version / abstract / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

This thesis focuses on the synthesis, properties and applications of two types of contorted organic molecules: contorted molecular ribbons and conjugated corrals. We utilized the power of reaction chemistry to writing information into conjugated molecules with contorted structures and studied “structure-property” relationships. The unique properties of the molecules were expressed in electronic and optoelectronic devices such as field-effect transistors, solar cells, photodetectors, etc. In Chapter 2, I describe the design and synthesis of a new graphene ribbon architecture that consists of perylenediimide (PDI) subunits fused together by ethylene bridges. We created a prototype series of oligomers consisting of the dimer, trimer, and tetramer. The steric congestion at the fusion point between the PDI units creates helical junctions, and longer oligomers form helical ribbons. Thin films of these oligomers form the active layer in n-type field effect transistors. UV−vis spectroscopy reveals the emergence of an intense long-wavelength transition in the tetramer. From DFT calculations, we find that the HOMO−2 to LUMO transition is isoenergetic with the HOMO to LUMO transition in the tetramer. We probe these transitions directly using femtosecond transient absorption spectroscopy. The HOMO−2 to LUMO transition electronically connects the PDI subunits with the ethylene bridges, and its energy depends on the length of the oligomer. In Chapter 3, I describe an efficiency of 6.1% for a solution processed non-fullerene solar cell using a helical PDI dimer as the electron acceptor. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor−acceptor interfaces, indicating that charge carriers are created from photogenerated excitons in both the electron donor and acceptor phases. Light-intensity-dependent current−voltage measurements suggested different recombination rates under short-circuit and open-circuit conditions. In Chapter 4, I discuss helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometers in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. In Chapter 5, I compare analogous cyclic and acyclic π-conjugated molecules as n-type electronic materials and find that the cyclic molecules have numerous benefits in organic photovoltaics. We designed two conjugated cycles for this study. Each comprises four subunits; one combines four electron-accepting, redox-active, diphenyl-perylenediimide subunits, and the other alternates two electron-donating bithiophene units with two diphenyl-perylenediimide units. We compare the macrocycles to acyclic versions of these molecules and find that, relative to the acyclic analogs, the conjugated macrocycles have bathochromically shifted UV-vis absorbances and are more easily reduced. In blended films, macrocycle-based devices show higher electron mobility and good morphology. All of these factors contribute to the more than doubling of the power conversion efficiency observed in organic photovoltaic devices with these macrocycles as the n-type, electron transporting material. This study highlights the importance of geometric design in creating new molecular semiconductors. In Chapter 6, I describe a new molecular design that enables high performance organic photodetectors. We use a rigid, conjugated macrocycle as the electron acceptor in devices to obtain high photocurrent and low dark current. We directly compare the macrocyclic acceptor devices to an acyclic control device; we find that the superior performance of the macrocycle originates from its rigid, conjugated, and cyclic structure. The macrocycle’s rigid structure reduces the number of charged defects originating from deformed sp2 carbons and covalent defects from photo/thermo-activation. With this molecular design we are able to suppress dark current density while retaining high responsivity in an ultra-sensitive non-fullerene organic photodetector. Importantly, we achieve a detectivity of ~10^14 Jones at near zero bias voltage. This is without the need for extra carrier blocking layers commonly employed in fullerene-based devices. Our devices are comparable to the best fullerene-based photodetectors, and the sensitivity at low working voltages (< 0.1 V) is a record for non-fullerene OPDs.