Growth and Characterization of III-V Semiconductor Materials for MOCVD Reactor Qualification and Process Control

Metalorganic chemical vapor deposition is examined as a technique for growing compound semiconductor structures. Material analysis techniques for characterizing the quality and properties of compound semiconductor material are explained and data from recent commissioning work on a newly installed reactor at the University of Illinois is presented.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Synthesis and structural stability of metal-organic frameworks

Metal-organic frameworks (MOFs) have attracted significant attention during the past decade due to their high porosity, tunable structures, and controllable surface functionalities. Therefore many applications have been proposed for MOFs. All of them however are still in their infancy stage and have not yet been brought into the market place. In this thesis, the background of the MOF area is first briefly introduced. The main components and the motifs of designing MOFs are summarized, followed by their synthesis and postsynthetic modification methods. Several promising application areas of MOFs including gas storage and separation, catalysis and sensing are reviewed. The current status of commercialization of MOFs as new chemical products is also summarized. Examples of the design and synthesis of two new MOF structures Eu(4,4′,4′′,4′′′-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid))·2H2O∙xDMF and Zn4O(azobenzene-4,4’-dicarboxylic acid)3∙xNMP are described. The first one contains free-base porphyrin centers and the second one has azobenzene components. Although the structures were synthesized as designed, unfortunately they did not possess the expected properties. The research idea to use MOFs as template materials to synthesize porous polymers is introduced. Several methods are discussed to grow PMMA into IRMOF-1 (Zn4O(benzene-1,4-dicarboxylate)3, IR stands for isoreticular) structure. High concentration of the monomers resulted in PMMA shell after MOF digestion while with low concentration of monomers no PMMA was left after digestion due to the small iii molecular weight. During the study of this chapter, Kitagawa and co-workers published several papers on the same topic, so this part of the research was terminated thereafter. Many MOFs are reported to be unstable in air due to the water molecules in air which greatly limited their applications. By incorporating a number of water repelling functional groups such as trifluoromethoxy group and methyl groups in the frameworks, the water stability of MOFs are shown to be significantly enhanced. Several MOFs inculding Banasorb-22 (Zn4O(2-trifluoromethoxybenzene-1,4-dicarboxylate)3), Banasorb-24 (Zn4O(2, 5-dimethylbenzene-1,4-dicarboxylate)3) and Banasorb-30 (Zn4O(2-methylbenzene-1,4-dicarboxylate)3) were synthesized and proved to have isostructures with IRMOF-1. Banasorb-22 was stable in boiling water steam for one week and Banasorb-30’s shelf life was over 10 months under ambient condition. For comparison, IRMOF-1’s structure collapses in air after a few hours to several days. Although MOF is a very popular research area nowadays, only a few studies have been reported on the mechanical properties of MOFs. Many of MOF’s applications involve high pressure conditions, so it is important to understand the behavior of MOFs under elivated pressures. The mechanical properties of IRMOF-1 and a new MOF structure Eu2(C12N2O4H6)3(DEF)0.87(H2O)2.13 were studied using diamond anvil cells at Advanced Photon Source. IRMOF-1 experienced an irriversible phase transtion to a nonporous phase followed by amorphization under high pressure. Eu2(C12N2O4H6)3(DEF)0.87(H2O)2.13 showed reversible compression under pressure up to 9.08GPa.

Growth and characterization of III-V compound semiconductor nanostructures by metalorganic chemical vapor deposition

Planar <110> GaAs nanowires and quantum dots grown by atmospheric MOCVD have been introduced to non-standard growth conditions such as incorporating Zn and growing them on free-standing suspended films and on 10° off-cut substrates. Zn doped nanowires exhibited periodic notching along the axis of the wire that is dependent on Zn/Ga gas phase molar ratios. Planar nanowires grown on suspended thin films give insight into the mobility of the seed particle and change in growth direction. Nanowires that were grown on the off-cut sample exhibit anti-parallel growth direction changes. Quantum dots are grown on suspended thin films and show preferential growth at certain temperatures. Envisioned nanowire applications include twin-plane superlattices, axial pn-junctions, nanowire lasers, and the modulation of nanowire growth direction against an impeding barrier and varying substrate conditions.

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.

Antimony-based type-II superlattice infrared detectors

Numerous applications within the mid- and long-wavelength infrared are driving the search for efficient and cost effective detection technologies in this regime. Theoretical calculations have predicted high performance for InAs/GaSb type-II superlattice structures, which rely on mature growth of III-V semiconductors and offer many levels of freedom in design due to band structure engineering. This work focuses on the fabrication and characterization of type-II superlattice infrared detectors. Standard UV-based photolithography was used combined with chemical wet or dry etching techniques in order to fabricate antinomy-based type-II superlattice infrared detectors. Subsequently, Fourier transform infrared spectroscopy and radiometric techniques were applied for optical characterization in order to obtain a detector's spectrum and response, as well as the overall detectivity in combination with electrical characterization. Temperature dependent electrical characterization was used to extract information about the limiting dark current processes. This work resulted in the first demonstration of an InAs/GaSb type-II superlattice infrared photodetector grown by metalorganic chemical vapor deposition. A peak detectivity of 1.6x10^9 Jones at 78 K was achieved for this device with a 11 micrometer zero cutoff wavelength. Furthermore the interband tunneling detector designed for the mid-wavelength infrared regime was studied. Similar results to those previously published were obtained.

Low temperature magneto-photoluminescence characterization of high purity gallium arsenide and indium phosphide

Low-temperature magneto-photoluminescence is a very powerful technique to characterize high purity GaAs and InP grown by various epitaxial techniques. These III-V compound semiconductor materials are used in a wide variety of electronic, optoelectronic and microwave devices. The large binding energy differences of acceptors in GaAs and InP make possible the identification of those impurities by low-temperature photoluminescence without the use of any magnetic field. However, the sensitivity and resolution provided by this technique rema1ns inadequate to resolve the minute binding energy differences of donors in GaAs and InP. To achieve higher sensitivity and resolution needed for the identification of donors, a magneto-photoluminescence system 1s installed along with a tunable dye laser, which provides resonant excitation. Donors 1n high purity GaAs are identified from the magnetic splittings of "two-electron" satellites of donor bound exciton transitions 1n a high magnetic field and at liquid helium temperature. This technique 1s successfully used to identify donors 1n n-type GaAs as well as 1n p-type GaAs in which donors cannot be identified by any other technique. The technique is also employed to identify donors in high purity InP. The amphoteric incorporation of Si and Ge impurities as donors and acceptors in (100), (311)A and (3ll)B GaAs grown by molecular beam epitaxy is studied spectroscopically. The hydrogen passivation of C acceptors in high purity GaAs grown by molecular beam epitaxy (MBE) and metalorganic chemical vapor deposition (MOCVD) 1s investigated using photoluminescence. Si acceptors ~n MBE GaAs are also found to be passivated by hydrogenation. The instabilities in the passivation of acceptor impurities are observed for the exposure of those samples to light. Very high purity MOCVD InP samples with extremely high mobility are characterized by both electrical and optical techniques. It is determined that C is not typically incorporated as a residual acceptor ~n high purity MOCVD InP. Finally, GaAs on Si, single quantum well, and multiple quantum well heterostructures, which are fabricated from III-V semiconductors, are also measured by low-temperature photoluminescence.

Carbon-carbon bond formation methods for the preparation of shape-persistent architectures

Carbon-rich, conjugated organic scaffolding is a popular basis for functional materials, especially for electronic and photonic applications. However, synthetic methods for generating these types of materials lack diversity and, in many cases, efficiency; the insistence of investigators focusing on the properties of the end product, rather than the process in which it was created, has led to the current state of the relatively homogeneous synthetic chemistry of functional organic materials. Because of this, there is plenty of room for improvement at the most basic level. Problems endemic to the preparation of carbon-rich scaffolding can, in many cases, be solved with modern advances in synthetic methodology. We seek to apply this synthesis-focused paradigm to solve problems in the preparation of carbon-rich scaffolds. Herein, the development and utilization of three methodologies: iridium-catalyzed arene C-H borylation; zinc- mediated alkynylations; and Lewis acid promoted Mo nitride-alkyne metathesis, are presented as improvements for the preparation of carbon-rich architectures. In addition, X-ray crystallographic analysis of two classes of compounds are presented. First, an analysis of carbazole-containing arylene ethynylene macrocycles showcases the significance of alkyl chain identity on solid-state morphology. Second, a class of rigid zwitterionic metal-organic compounds display an unusual propensity to crystallize in the absence of inversion symmetry. Hirshfeld surface analysis of these crystalline materials demonstrates that subtle intermolecular interactions are responsible for the overall packing motifs in this class of compounds.

Chemical and physical effects of ultrasound: sonoluminescence and materials

When a liquid is irradiated with ultrasound, acoustic cavitation (the formation, growth, and implosive collapse of bubbles in liquids irradiated with ultrasound) generally occurs. This is the phenomenon responsible for the driving of chemical reactions (sonochemistry) and the emission of light (sonoluminescence). The implosive collapse of bubbles in liquids results in an enormous concentration of sound energy into compressional heating of the bubble contents. Therefore, extreme chemical and physical conditions are generated during cavitation. The study of multibubble sonoluminescence (MBSL) and single-bubble sonoluminescence (SBSL) in exotic liquids such as sulfuric acid (H2SO4) and phosphoric acid (H3PO4) leads to useful information regarding the intracavity conditions during bubble collapse. Distinct sonoluminescing bubble populations were observed from the intense orange and blue-white emissions by doping H2SO4 and H3PO4 with sodium salts, which provides the first experimental evidence for the injected droplet model over the heated-shell model for cavitation. Effective emission temperatures measured based on excited OH• and PO• emission indicate that there is a temperature inhomogeneity during MBSL in 85% H3PO4. The formation of a temperature inhomogeneity is due to the existence of different cavitating bubble populations: asymmetric collapsing bubbles contain liquid droplets and spherical collapsing bubbles do not contain liquid droplets. Strong molecular emission from SBSL in 65% H3PO4 have been obtained and used as a spectroscopic probe to determine the cavitation temperatures. It is found that the intracavity temperatures are dependent on the applied acoustic pressures and the thermal conductivities of the dissolved noble gases. The chemical and physical effects of ultrasound can be used for materials synthesis. Highly reactive species, including HO2•, H•, and OH• (or R• after additives react with OH•), are formed during aqueous sonolysis as a consequence of the chemical effects of ultrasound. Reductive species can be applied to synthesis of water-soluble fluorescent silver nanoclusters in the presence of a suitable stabilizer or capping agent. The optical and fluorescent properties of the Ag nanoclusters can be easily controlled by the synthetic conditions such as the sonication time, the stoichiometry of the carboxylate groups to Ag+, and the polymer molecular weight. The chemical and physical effects of ultrasound can be combined to prepare polymer functionalized graphenes from graphites and a reactive solvent, styrene. The physical effects of ultrasound are used to exfoliate graphites to graphenes while the chemical effects of ultrasound are used to induce the polymerization of styrene which can then functionalize graphene sheets via radical coupling. The prepared polymer functionalized graphenes are highly stable in common organic solvents like THF, CHCl3, and DMF. Ultrasonic spray pyrolysis (USP) is used to prepare porous carbon spheres using energetic alkali propiolates as the carbon precursors. In this synthesis, metal salts are generated in situ, introducing porous structures into the carbon spheres. When different alkali salts or their mixtures are used as the precursor, carbon spheres with different morphologies and structures are obtained. The different precursor decomposition pathways are responsible for the observed structural difference. Such prepared carbon materials have high surface area and are thermally stable, making them potentially useful for catalytic supports, adsorbents, or for other applications by integrating other functional materials into their pores.