This thesis presents the development of III-nitride materials for deep-ultraviolet (DUV) light emitting devices. The goal of this research is to develop a DUV laser diode (LD) operating at room temperature. Epitaxial structures for these devices are grown by metalorganic chemical vapor deposition (MOCVD) and several material analysis techniques were employed to characterize these structures such as atomic force microscopy, electroluminescence, Hall-effect measurement, photoluminescence, secondary ion mass spectrometry, transmission electron microscopy, transmission line measurement, and X-ray diffraction. Each of these will be discussed in detail. The active regions of III-nitride based UV emitters are composed of AlxGa1-xN alloys, the bandgap of which can be tuned from 3.4 eV to 6.2 eV, which allows us to attain the desired wavelength in the DUV by engineering the molar fraction of aluminum and gallium. In order to emit photons in the DUV wavelength range (> 4.1 eV), high aluminum molar fraction AlxGa1-xN alloys are required. Since aluminum has very low ad-atom mobility on the growth surface, a very low group V to group III precursor ratio (known as V/III ratio), high growth temperature, and low growth pressure is required to form a smooth surface and subsequently abrupt heterointerfaces. The first part of this work focuses on developing high-quality multi-quantum well structures using high aluminum molar fraction ([Al] > 60%) AlxGa1-xN alloys. Optically pumped DUV lasers were demonstrated with threshold power density as low as 250 kW/cm² for the emission wavelength as short as 248.3 nm. Transverse electric (TE) -like emission dominates when the lasers were operating above threshold power density, which suggests the diode design requires the active region to be fully strained to promote better confinement of the optical mode in transverse direction. The second phase of this project is to achieve an electrically driven injection diode laser. Owing to their large bandgap, low intrinsic carrier concentration, and relatively high dopant activation energy, the nature of these high aluminum molar fraction materials are highly insulating; therefore, efficiently transport carriers into active region is one of the main challenges. Highly conducting p-type material is especially difficult to achieve because the activation energy for magnesium, a typical dopant, is relatively large and some of the acceptors are compensated by the hydrogen during the growth. Furthermore, due to the lack of a large work function material to form a p-type ohmic contact, the p-contact layer design is limited to low aluminum molar fraction material or gallium nitride. Besides the fabrication challenges, these low aluminum molar fraction materials are not transparent to the laser wavelength causing relatively high internal loss (αi). In this work, an inverse tapered p-waveguide design is employed to transport holes to active region efficiently while the graded-index separate-confinement heterostructure (GRINSCH) is employed for the active region design. Together, a multi-quantum well (MQW) ultraviolet emitter was demonstrated.

No description available.

Doctor of Philosophy / Department of Physics / Hongxing Jiang / The optical and structural properties of Er-doped GaN/InGaN materials and devices synthesized by metal organic chemical vapor deposition (MOCVD) were investigated. Er-doped GaN via MOCVD emits a strong photoluminescence (PL) emission at 1.54 um using both above and below-bandgap excitation. In contrast to other growth methods, MOCVD-grown Er-doped GaN epilayers exhibit virtually no visible emission lines. A small thermal quenching effect, with only a 20% decrease in the integrated intensity of the 1.54 um PL emission, occurred between 10 and 300 K. The dominant bandedge emission of Er-doped GaN at 3.23 eV was observed at room temperature, which is red-shifted by 0.19 eV from the bandedge emission of undoped GaN. An activation energy of 191 meV was obtained from the thermal quenching of the integrated intensity of the 1.54 um emission line. It was observed that surface morphology and 1.54 um PL emission intensity was strongly dependent upon the Er/NH3 flow rate ratio and the growth temperature. XRD measurements showed that the crystalline ordering of the (002) plane was relatively unperturbed for the changing growth environment. Least-squares fitting of 1.54 um PL measurements from Er-doped GaN of different growth temperatures was utilized to determine a formation energy of 1.82 ± 0.1 eV for the Er-emitting centers. The crystalline quality and surface morphology of Er-doped InGaN (5% In fraction) was nearly identical to that of Er-doped GaN, yet the PL intensity of the 1.54 um emission from Er-doped InGaN (5% In fraction) was 16 x smaller than that of Er-doped GaN. The drop in PL intensity is attributed to the much lower growth temperature in conjunction with the high formation energy of the Er- emitting centers. Er-doped InGaN grown at fixed growth temperature with different growth pressures, NH3 flow rates, and Ga flow rates was also investigated, and showed that increased In fractions also resulted in a smaller 1.54 um PL intensity. Er-doped InGaN p-i-n diodes were synthesized and tested. The electroluminescence (EL) spectra under forward bias shows strong Er based emission in the infrared and visible region. The different emission lines from EL spectra in contrast to PL spectra implies different excitation methods for the Er based emission in the p-i-n diode than in the PL excited epilayer.

This thesis describes the design, fabrication and characterization of AlGaN/GaN Heterostructure Field E ect Transistors (HFETs) grown by a Metal Organic Chemical Vapor Deposition (MOCVD) on sapphire substrates. The objective of this research is to develop AlGaN/GaN power devices with high breakdown voltage (greater than 1 kV) and low turn-on resistance. Various characteristics such as current drive (Idss), transconductance (gm) and threshold voltage (Vth) have also been measured and the results have been discussed. Two major challenges with the development of high breakdown voltage AlGaN/GaN HFETs in the past have been high material defect density and non-optimized fabrication technologies which gives rise to bu er leakage and surface leakage, respectively. In this thesis, mesa isolation, ohmic and gate metal contacts, and passivation techniques, have been discussed to improve the performance of these power transistors in terms of low contact resistance and low gate leakage. The relationship between breakdown voltage and Rds(ON)A with respect to the gate-drain length (Lgd) is also discussed. First, unit cell devices were designed (two-fingered cells with Wg = 100, 300, 400 m) and characterized, and then they were extended to form large area devices (upto Wg = 40 mm). The design goals were classied into three parts: - High Breakdown Voltage: This was achieved by designing devices with variations in Lgd, - Low turn-on resistance: This was achieved by optimizing the annealing temperatures as well as incorporating additional thick metal pads, as well as optimizing the passivation etch recipe, - Low Gate Leakage: The gate leakage was reduced signicantly by using a gate metal with a larger barrier height. All devices with Lgd larger than 10 m exhibited excellent breakdown voltage characteristics of over 800 V, and it progressed as the Lgd increased. The turn-on resistance was also reduced signicantly below 20 m-cm2, for devices with Lgd = 15, 25, and 20 m. The gate leakage was measured for all devices upto 200 V, and was in the range of 10-100 nA, which is one of the best values reported for multi-ngered devices with Lgd in the range of 2.4-5 mm. Some of the key challenges faced in fabrication were determining a better gate metal layer to reduce gate leakage, optimizing the passivation via etch recipe, and reducing surface leakage.

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Group III-Nitrides (GaN, InN & AlN) are considered one of the most important class of semiconducting materials after Si and GaAs. The excellent optical and electrical properties of these nitrides result in numerous applications in lighting, lasers, and high-power/high-frequency devices. Due to the lack of cheap bulk III- Nitride substrates, GaN based devices have been developed on foreign substrates like Si, sapphire and SiC. These technologies have been predominantly developed on the so called Ga-polarity epitaxial stacks with growth in the [0001] direction of GaN. It is this orientation that grows most easily on sapphire by metal organic chemical vapor deposition (MOCVD), the most common combination of substrate and deposition method used thus far. The opposite [000¯1] or N-polar orientation, very different in properties due to the lack of an inversion centre, offers several ad- vantages that could be exploited for better electronic and optoelectronic devices. However, its growth is more challenging and needs better understanding. The aim of the work reported in this dissertation was a systematic investigation of the relation between the various growth parameters which control polarity, surface roughness and mosaicity of GaN on non-miscut sapphire (0001) wafers for power electronics and lighting applications, with emphasis on the realization of N-polar epitaxial layers. GaN is grown on sapphire (0001) in a two-step process, which involves the deposition of a thin low temperature GaN nucleation layer (NL) on surface modified sapphire followed by the growth of high temperature device quality GaN epitaxial layer. The processing technique used is MOCVD. Various processing methods for synthesis of GaN layers are described with particular em- phasis on MOCVD method. The effect of ex situ cleaning followed by an in situ cleaning on the surface morphology of sapphire (0001) wafers is discussed. The characterization tools used in this dissertation for studying the chemical bond nature of nitrided sapphire surface and microstructural evolution (morphological and structural) of GaN layers are described in detail. The effect of nitridation temperature (TN) on structural transformation of non- miscut sapphire (0001) surface has been explored. The structural evolution of nitrided layers at different stages of their process like as grown stage and thermal annealing stage is investigated systematically. The chemical bond environment information of the nitrided layers have been examined by x-ray photoelectron spectroscopy (XPS). It is found that high temperature nitridation (TN ≥ 800oC) results in an Al-N tetrahedral bond environment on sapphire surface. In contrast, low temperature nitridation (TN = 530oC) results in a complex Al-O-N environment on sapphire surfaces. Microstructural evolution of low temperature GaN NLs has been studied at every stage of processing by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Surface roughness evolution and island size distribution of NLs measured from AFM are discussed. It is found that NLs processed on sapphire wafers nitrided at (TN ≥ 800oC) showed strong wurtzite [0002] orientation with sub-nanometre surface roughness. In contrast, NLs processed at (TN = 530oC) showed zinc blende phase in the as grown stage with higher surface roughness, but acquired a greater degree of wurtzite [0002] orientation after thermal annealing prior to high temperature GaN growth. Polarity, surface quality and crystal quality of subsequently grown high temperature GaN epitaxial layers is described in relation to the structure of the trans- formed nitrided layers. Higher nitridation temperatures (TN ≥ 800oC) consistently yield N-polar GaN whereas lower nitridation temperatures (TN = 530oC) yield Ga-polar GaN. It is found that the relative O atom concentration levels in nitrided layers control the density of inversion domains in N-polar GaN. The effect of various growth parameters (NH3 flow rate, growth temperature, NL thickness) on surface morphology and mosaicity of both Ga & N-polar GaN layers is discussed in detail. We report device quality N-polar GaN epitaxial layers on non-miscut sapphire (0001) wafers by careful optimization of growth temperature. It is found that lower growth temperatures (800oC) are favorable for obtaining smooth N- polar GaN layers. In contrast, N-polar GaN layers grown at higher temperatures (1000 to 1080oC) are rough with hexagonal hillocks.

High quality ammonium oxofluorotitanate discoid crystal is successfully grown on glass with an aqueous solution of ammonium hexafluorotitanate and boric acid at the molar ratio of 0.6. The concentration of hydrofluoric acid is less on the glass substrate surface and enhances the ammonium oxofluorotitanate nucleation growth. The growth rate is much higher than that grown on dioctadecyldimethylammonium. From the examinations of X-ray diffraction and high-resolution transmission electron microscopy, the crystal shows high crystalline quality and uniformity. Each titanium oxide octahedral is linked with fluorine and nitrogen atoms. Therefore, ammonium oxofluorotitanate has high potential to be thermally decomposed into high crystalline fluorine and nitrogen co-doped titanium oxide. A simple process for the preparation of nanocrystalline anatase phase titanium oxide converted from ammonium oxofluorotitanate by thermal treatment was developed. The nanocrystalline anatase phase titanium oxide shows a large bandgap reduction due to the co-doping of high concentrations of fluorine and nitrogen. Due to the excellent nanocrystalline quality and the co-doping of higher concentrations of fluorine and nitrogen at the thermal treatment temperature of 800 OC, it is 1.3 times the photocatalytic activities of P-25 due to the visble region usage of Hg lamp light source. The 11.2 times the visible photocatalytic activities of P-25 using blue light-emitting diode as the light source is obtained from thermal treatment temperature of 600 OC. There is one to one correspondence between carrier lifetime and photocatalytic activity. As a result, a highly reactive and visible-light-driven photocatalysis is achieved. The heterostructure of zinc selenide/titanium oxide and zinc sulfide/titanium oxide were prepared by metal-organic chemical vapor deposition on the above-prepared titanium oxide. The energy bandgap of zinc sulfide is much larger than that of titanium oxide and can act as a window for titanium oxide. It would not hinder titanium oxide absorption and preserve the role of fluorine and nitrogen co-doping. The energy bandgap of zinc selenide is near the maximum intensity of solar spectrum and acts as a sensitizer of titanium oxide. The lifetime of electron and hole pairs of heterostructure are about 240 and 207 nsec, which are longer than 65 nsec of titanium oxide prepared at 800 oC thermal treatment. Their photocatalytic activities are further improved to 2.0 and 1.5 times higher than that of commercial P-25. The photocatalysis of titanium oxide is very sensitive to the surface states. Titanium oxide surface defects can act as trapping sites for photo-induced holes and facilitate the separation of photo-induced carriers. Zinc selenide and zinc sulfide can passivate the surface well. It may say that titanium oxide surface defects removal has a negative impact. The density, height, diameter, PL wavelength and intensity of zinc selenide self-assembled quantum dots grown on zinc sulfide/gallium arsenide with the zinc sulfide thickness from 15 to 160 nm are studied. For a fixed 30 sec zinc selenide self-assembled quantum dots growth, it cannot be formed with the zinc sulfide thickness below 15 nm due to the close lattice match between zinc sulfide and gallium arsenide. The zinc sulfide/gallium arsenide is fully lattice relaxed with the zinc sulfide thickness higher than 130 nm examined by X-ray diffraction. The higher quality and density of zinc selenide self-assembled quantum dots can be obtained on zinc sulfide/gallium arsenide with the zinc sulfide thickness far beyond its critical thickness. The maximum zinc selenide self-assembled quantum dots density of 4.9 x 109 cm-2 with the strongest photoluminescence intensity is obtained at the zinc sulfide/gallium arsenide thickness of 130 nm. Clusters are formed on the surface of zinc selenide/gallium arsenide. The selenium segregation is the main mechanism for the formation of clusters. The dislocations will enhance the selenium segregation. Higher zinc selenide cluster corresponds to higher density of dislocations. The non-spherical cluster is formed from the mergence of the two clusters. High quality zinc oxide rods and zinc hydroxide slices are successfully grown on gallium arsenide with the aqueous solution of zinc nitrate and hexamethylenetetramine. The growth can be controlled by the appropriate nitric acid concentration incorporation in the solution. After thermal annealing, the zinc oxide slices transformed from zinc hydroxide slices can contribute much higher photocatalytic activity to 1.2 times to P-25.

No description available.

Despite enormous efforts and investments, the efficiency of InGaN-based green and yellow-green light emitters remains relatively low, and that limits progress in developing full color display, laser diodes, and bright light sources for general lighting. The low efficiency of light emitting devices in the green-to-yellow spectral range, also known as the “Green Gap”, is considered a global concern in the LED industry. The polar c-plane orientation of GaN, which is the mainstay in the LED industry, suffers from polarization-induced separation of electrons and hole wavefunctions (also known as the “quantum confined Stark effect”) and low indium incorporation efficiency that are the two main factors that contribute to the Green Gap phenomenon. One possible approach that holds promise for a new generation of green and yellow light emitting devices with higher efficiency is the deployment of nonpolar and semi-polar crystallographic orientations of GaN to eliminate or mitigate polarization fields. In theory, the use of other GaN planes for light emitters could also enhance the efficiency of indium incorporation compared to c-plane. In this thesis, I present a systematic exploration of the suitable GaN orientation for future lighting technologies. First, in order to lay the groundwork for further studies, it is important to discuss the analysis of processes limiting LED efficiency and some novel designs of active regions to overcome these limitations. Afterwards, the choice of nonpolar orientations as an alternative is discussed. For nonpolar orientation, the (1-100)-oriented (m-plane) structures on patterned Si (112) and freestanding m-GaN are studied. The semi-polar orientations having substantially reduced polarization field are found to be more promising for light-emitting diodes (LEDs) owing to high indium incorporation efficiency predicted by theoretical studies. Thus, the semi-polar orientations are given close attention as alternatives for future LED technology. One of the obstacles impeding the development of this technology is the lack of suitable substrates for high quality materials having semi-polar and nonpolar orientations. Even though the growth of free-standing GaN substrates (homoepitaxy) could produce material of reasonable quality, the native nonpolar and semi-polar substrates are very expensive and small in size. On the other hand, GaN growth of semi-polar and nonpolar orientations on inexpensive, large-size foreign substrates (heteroepitaxy), including silicon (Si) and sapphire (Al2O3), usually leads to high density of extended defects (dislocations and stacking faults). Therefore, it is imperative to explore approaches that allow the reduction of defect density in the semi-polar GaN layers grown on foreign substrates. In the presented work, I develop a cost-effective preparation technique of high performance light emitting structures (GaN-on-Si, and GaN-on-Sapphire technologies). Based on theoretical calculations predicting the maximum indium incorporation efficiency at θ ~ 62º (θ being the tilt angle of the orientation with respect to c-plane), I investigate (11-22) and (1-101) semi-polar orientations featured by θ = 58º and θ = 62º, respectively, as promising candidates for green emitters. The (11-22)-oriented GaN layers are grown on planar m-plane sapphire, while the semi-polar (1-101) GaN are grown on patterned Si (001). The in-situ epitaxial lateral overgrowth techniques using SiNx nanoporous interlayers are utilized to improve the crystal quality of the layers. The data indicates the improvement of photoluminescence intensity by a factor of 5, as well as the improvement carrier lifetime by up to 85% by employing the in-situ ELO technique. The electronic and optoelectronic properties of these nonpolar and semi-polar planes include excitonic recombination dynamics, optical anisotropy, exciton localization, indium incorporation efficiency, defect-related optical activities, and some challenges associated with these new technologies are discussed. A polarized emission from GaN quantum wells (with a degree of polarization close to 58%) with low non-radiative components is demonstrated for semi-polar (1-101) structure grown on patterned Si (001). We also demonstrated that indium incorporation efficiency is around 20% higher for the semi-polar (11-22) InGaN quantum wells compared to its c-plane counterpart. The spatially resolved cathodoluminescence spectroscopy demonstrates the uniform distribution of indium in the growth plane. The uniformity of indium is also supported by the relatively low exciton localization energy of Eloc = 7meV at 15 K for these semi-polar (11-22) InGaN quantum wells compared to several other literature reports on c-plane. The excitons are observed to undergo radiative recombination in the quantum wells in basal-plane stacking faults at room temperature. The wurtzite/zincblende electronic band-alignment of BSFs is proven to be of type II using the time-resolved differential transmission (TRDT) method. The knowledge of band alignment and degree of carrier localization in BSFs are extremely important for evaluating their effects on device properties. Future research for better understanding and potential developments of the semi-polar LEDs is pointed out at the end.